Under de senaste decennierna har i många länder, inkluderat Sverige, långt gångna planer utvecklats för ett djupförvar av högaktivt kärnavfall. Som en del i det svenska förvarskonceptet skall avfallet inneslutas i kopparkapslar som omslutes av återfyllnadsmaterial med mycket låg genomsläpplighet av vatten. Dessutom skall kapslarna förläggas på ca 500 meters djup i granitberggrunden, vilken fungerar som en naturlig barriär för transport av radionuklider till markytan. Dessa naturliga och konstruerade barriärer väljs och utformas så att förvarets funktion kan säkras under hundra tusentals år. En viktig fråga för säkerhetsanalysen för ett sådant förvar är utvecklingen av redoxförhållandena över långa tider. Korrosionen av kopparkapslarna går fortare under oxiderande förhållanden och rörligheten hos frisläppta radionuklider ökar. I den första delen av avhandlingen studerades förmågan hos berget att upprätthålla reducerande förhållanden på förvarsdjupet över långa tider. En modellstruktur har utvecklats med målet att ta hänsyn till alla processer som bedömts viktiga för utarmning av inträngande syre från markytan över långa tider. Förenklingar introducerades så att transparenta analytiska lösningar kunde erhållas som förenklar utvärdering av resultat och tillåter identifiering av osäkra parametrar. Komplexa system löstes numeriskt för fall då analytiska lösningar ej kunde erhållas, samt för att validera förenklingar som ligger till grund för de analytiska lösningarna. Resultat redovisades för rådande förhållanden samt för förhållanden som bedömdes rimliga under smältfasen av en glaciationsperiod. Det visade sig att de hydrauliska egenskaperna har stor påverkan på inträngningsdjupet av syre längs flödesvägar i berget. Kvoten mellan den flödesvätta ytan och flödet visade sig vara en viktig parameter som bestämmer omfattningen av interaktionen mellan löst syre i grundvattnet och reducerande mineral i berget. Resultaten visar att för korta tider, beroende på mängd reducerande mineral och reaktionshastighet, kan kemisk reaktionskinetik bestämma förbrukningshastigheten av syre. För längre tider begränsas förbrukningen av intern diffusion i stora partiklar och bergmatrisen. Det visade sig att hänsyn måste tas till många osäkerheter för att kunna göra tillförlitliga kvantitativa uppskattningar av omfattningen av syreinträngningen. I den andra delen av avhandlingen undersöktes konsekvenserna av inträngande syre på korrosion av kopparkapslarna. En mekanism föreslogs också för bildande av sulfid nära kapseln. Sulfid är en annan korrodent som kan bildas mikrobiellt i reducerande miljöer från sulfat och en organisk reduktant såsom metan. Beräkningarna visar att mer än 50 kg av koppar inte är sannolikt att korrodera över en miljon år. / Advanced plans for the construction of a deep geological repository for highly radioactive wastes from nuclear power plants have evolved during the past decades in many countries including Sweden. As part of the Swedish concept, the waste is to be encapsulated in canisters surrounded by low permeability backfill material. The copper canisters will be deposited at around 500 metres depth in granitic rock, which acts as a natural barrier for the transport of radionuclides to the ground surface. These natural and engineered barriers are chosen and designed to ensure the safety of the repository over hundred of thousands of years. One issue of interest for the safety assessment of such a repository is the redox evolution over long times. An oxidising environment would enhance the corrosion of the copper canisters, and increases the mobility of any released radionuclides. In the first part of the present thesis, the ability of the host rock to ensure a reducing environment at repository depth over long times was studied. A model framework was developed with the aim to capture all processes that are deemed to be important for the scavenging of intruding oxygen from the ground surface over long times. Simplifications allowing for analytical solutions were introduced for transparency reasons so that evaluation of results is straight-forward, and so that uncertain parameter values easily can be adjusted. More complex systems were solved numerically for cases when the analytical simplifications are not applicable, and to validate the simplifications underlying the analytical solutions. Results were presented for prevailing present day conditions as well as for conditions deemed to be likely during the melting phase of a period of glaciation. It was shown that the hydraulic properties have a great influence on the oxygen intrusion length downstream along flow-paths in the rock. An important parameter that determines the extent of interaction between the dissolved oxygen and the reducing minerals in the rock was shown to be the flow-wetted surface to flow-rate ratio. The results show that for an initial period of time, depending on the amount of reducing minerals and reaction rates, chemical reaction kinetics may control the rate of the overall depletion of oxygen. For longer times, internal diffusion resistance in large particles or in the rock matrix become rate limiting for the overall process. It was found that there are many uncertainties that have to be considered in order to make reliable quantitative predictions on the extent of oxygen intrusion. In the second part of the thesis, the impact of intruding oxygen on the corrosion of the copper canisters was explored. Also, a mechanism for the production of sulphide close to the deposition holes was studied. Sulphide is another corroding agent that may be produced microbially in a reducing environment from sulphate in the presence of organic reductants such as methane. From calculation results it was found that corrosion of more than 50 kg of copper is not likely over a period of one million years / QC 20100818

Fluids play a vital role in essentially all geologic environments and processes, and are the principal media of heat and mass transfer in the Earth. The properties of geologic fluids can be diverse, as fluids occur at conditions ranging from ambient temperatures and pressures at Earth's surface, to extreme temperatures and pressures in Earth's deep interior. Regardless the wide ranges of conditions at which geologic fluids occur, fluid properties are described and governed by the same fundamental thermodynamic relationships. Thus, application of thermodynamic principles and methods allows us to decipher the properties and roles of geologic fluids, to help understand geologic processes. Fluid inclusions in minerals provide one of the best available tools to study the compositions of geological fluids. Compositions of fluid inclusions can be determined from microthermometric measurements, based on the vapor-saturated liquidus conditions of model chemical systems, or by various microanalytical techniques. The vaporsaturated liquidus relations of the system H2O-NaCl-CaCl2 have been modeled to allow estimation of fluid inclusion compositions by either microthermometric or microanalytical methods. Carbon capture and storage (CCS) in deep saline formations represents one option for reducing anthropogenic CO2 emissions into Earth's atmosphere. Availability of storage volume in deep saline formations is a significant component of injection and storage planning. Investigation of the volumetric properties of CO2, brine and CO2-saturated brine reveals that storage volume requirements are minimized when CO2 dissolves into brine. These results suggest that a protocol involving brine extraction, CO2 dissolution and re-injection may optimize CCS in deep saline formations. Numerical modeling of quartz dissolution and precipitation in a sub-seafloor hydrothermal system was used to understand the role of fluid-phase immiscibility ("boiling") on quartz-fluid interactions, and to predict where in the system quartz could deposit and trap fluid inclusions. The spatial distribution of zones of quartz dissolution and precipitation is complex, owing to the many inter-related factors controlling quartz solubility. Immiscibility exerts a strong control over the occurrence of quartz precipitation in the deeper regions of fluid circulation. / Ph. D.

Orientador: Marlene Cristina Alves / Resumo: A compactação do solo em sistemas plantio direto (SPD) tem comprometido a sua sustentabilidade. Para contornar esse problema, a escarificação mecânica e a manutenção da cobertura vegetal são sugeridas como práticas de manejo a fim de restabelecer as condições ideais de cultivo. Assim, o objetivo deste trabalho foi avaliar o efeito a curto prazo da escarificação e do uso de diferentes plantas de cobertura na manutenção do SPD envolvendo as culturas do arroz de “terras altas” e feijão de “inverno”). O trabalho foi desenvolvido em Selvíria, MS em 2014/15 e 2015/16, em um Latossolo Vermelho Distrófico de textura argilosa. Utilizou-se o delineamento em blocos casualizados disposto em parcelas subdivididas, tendo nas parcelas as condições da superfície do solo em SPD (com e sem escarificação mecânica) e nas subparcelas as plantas de cobertura (pousio, Cajanus cajan, Crotalaria juncea, Urochloa ruziziensis (Syn. Brachiaria ruziziensis) e Pennisetum glaucum), com quatro repetições, cultivadas com arroz e feijão. Foram avaliadas as características fitotécnicas das culturas e atributos físicos e químicos do solo em quatro camadas (0 a 0,05; 0,05 a 0,10; 0,10 a 0,20 e 0,20 a 0,40 m). Realizou-se a análise de variância e teste de Tukey a 5%de probabilidade para comparação de médias. Além disso, na camada de 0 a 0,05 m do solo também foram analisadas as características das nanopartículas e nanoestruturas do solo. Para essas análises incluiu-se o solo de Cerrado remanescente para comparaçã... (Resumo completo, clicar acesso eletrônico abaixo) / Abstract: Soil compaction in no-tillage systems (NTS) affects the sustainability of this management. To overcome the problem, mechanical chiseling and maintenance of the cover crop were suggested as management practices reestablishing ideal cultivation conditions. Thus, the objective of this study was to evaluate the short-term effect of mechanical chiseling and the use of different cover crops in the maintenance of NTS involving as crops "dryland” rice and "winter" common bean. The experiment was conducted in Selvíria, state of Mato Grosso do Sul, Brazil, during the 2014/15 and 2015/16 growing season, on a typical clayey dystrophic Red Latosol, with experiment was evaluated in a randomized block design in split plots, with the main plots as SPD soil surface conditions (with and without mechanical chiseling) and in the subplots as cover crop (fallow, Cajanus cajan, Crotalaria juncea, Urochloa ruziziensis and Pennisetum glaucum), with four replications, cultivated with “dryland” rice and "winter" common bean. The agronomic characteristics of the crops and soil physical and chemical attributes in four layers (0 a 0.05; 0.05 a 0.10; 0.10 a 0.20 e 0.20 a 0.40 m). The analysis of variance and Tukey's test were performed at a 5% probability for comparison of average. In addition, treatments of the 0 to 0.05 m layer of the soil were also compared to the natural closed area, through the conventional chemical and physical properties and characteristics of its nanoparticles and nanostructures. F... (Complete abstract click electronic access below) / Doutor

Submitted by EPITÁCIO JOSÉ DE SOUZA null (epitacio.agro@gmail.com) on 2018-03-15T22:10:40Z No. of bitstreams: 1 NANOTECNOLOGIA APLICADA A AVALIAÇÃO FÍSICA DE UM LATOSSOLO DE CERRADO SOB SISTEMAS DE SUCESSÃO DE CULTURAS EM PLANTIO DIRETO .pdf: 4786904 bytes, checksum: 2e74d65cc0fde9399a953d88dd0a155e (MD5) / Approved for entry into archive by Cristina Alexandra de Godoy null (cristina@adm.feis.unesp.br) on 2018-03-16T19:38:28Z (GMT) No. of bitstreams: 1 souza_ej_dr_ilha.pdf: 4786904 bytes, checksum: 2e74d65cc0fde9399a953d88dd0a155e (MD5) / Made available in DSpace on 2018-03-16T19:38:28Z (GMT). No. of bitstreams: 1 souza_ej_dr_ilha.pdf: 4786904 bytes, checksum: 2e74d65cc0fde9399a953d88dd0a155e (MD5) Previous issue date: 2018-01-18 / Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq) / A compactação do solo em sistemas plantio direto (SPD) tem comprometido a sua sustentabilidade. Para contornar esse problema, a escarificação mecânica e a manutenção da cobertura vegetal são sugeridas como práticas de manejo a fim de restabelecer as condições ideais de cultivo. Assim, o objetivo deste trabalho foi avaliar o efeito a curto prazo da escarificação e do uso de diferentes plantas de cobertura na manutenção do SPD envolvendo as culturas do arroz de “terras altas” e feijão de “inverno”). O trabalho foi desenvolvido em Selvíria, MS em 2014/15 e 2015/16, em um Latossolo Vermelho Distrófico de textura argilosa. Utilizou-se o delineamento em blocos casualizados disposto em parcelas subdivididas, tendo nas parcelas as condições da superfície do solo em SPD (com e sem escarificação mecânica) e nas subparcelas as plantas de cobertura (pousio, Cajanus cajan, Crotalaria juncea, Urochloa ruziziensis (Syn. Brachiaria ruziziensis) e Pennisetum glaucum), com quatro repetições, cultivadas com arroz e feijão. Foram avaliadas as características fitotécnicas das culturas e atributos físicos e químicos do solo em quatro camadas (0 a 0,05; 0,05 a 0,10; 0,10 a 0,20 e 0,20 a 0,40 m). Realizou-se a análise de variância e teste de Tukey a 5%de probabilidade para comparação de médias. Além disso, na camada de 0 a 0,05 m do solo também foram analisadas as características das nanopartículas e nanoestruturas do solo. Para essas análises incluiu-se o solo de Cerrado remanescente para comparação com os tratamentos estudados. As nanopartículas (< 200nm) foram extraídas e caracterizadas por microscopia eletrônica de transmissão (MET) e espectrometria de infravermelho (FTIR). Os resultados obtidos foram avaliados por meio da análise dos componentes principais e agrupamentos hierárquicos. As plantas de cobertura e a escarificação não influenciaram a produtividade do arroz de “terras altas “e do feijão de “inverno” após dois anos de cultivo. O estudo das nanopartículas e nanoestruturas mostrou-se sensível as alterações promovidas pelo uso da escarificação e das plantas de cobertura, apresentando assim potencial para ser uma ferramenta suplementar indicadora de qualidade do solo. O fósforo (P) foi o atributo químico mais influenciado pelas práticas de manejo pela sucessão com milheto (Pennisetum glaucum) sem escarificação nas duas camadas superficiais e nas demais camadas pela sucessão Urochloa ruziziensis (Syn. Brachiaria ruziziensis). Os atributos físicos e químicos do solo combinados com a caracterização de nanopartículas permitiram identificar que o milheto (Pennisetum glaucum) sem escarificação como mudanças estáveis para a manutenção do SPD. As características geométricas e químicas das nanopartículas auxiliam na identificação de mudanças causadas pelas práticas de manejos sobre os indicadores físicos e químicos da qualidade do solo. A contribuição das plantas de cobertura para a manutenção do SPD está ligada diretamente pela adição de matéria orgânica do solo (MOS). Deste modo contribuindo para as melhorias dos atributos químicos, físicos e influenciaram no comportamento das nanopartículas e nanoestrutura do solo. / Soil compaction in no-tillage systems (NTS) affects the sustainability of this management. To overcome the problem, mechanical chiseling and maintenance of the cover crop were suggested as management practices reestablishing ideal cultivation conditions. Thus, the objective of this study was to evaluate the short-term effect of mechanical chiseling and the use of different cover crops in the maintenance of NTS involving as crops "dryland” rice and "winter" common bean. The experiment was conducted in Selvíria, state of Mato Grosso do Sul, Brazil, during the 2014/15 and 2015/16 growing season, on a typical clayey dystrophic Red Latosol, with experiment was evaluated in a randomized block design in split plots, with the main plots as SPD soil surface conditions (with and without mechanical chiseling) and in the subplots as cover crop (fallow, Cajanus cajan, Crotalaria juncea, Urochloa ruziziensis and Pennisetum glaucum), with four replications, cultivated with “dryland” rice and "winter" common bean. The agronomic characteristics of the crops and soil physical and chemical attributes in four layers (0 a 0.05; 0.05 a 0.10; 0.10 a 0.20 e 0.20 a 0.40 m). The analysis of variance and Tukey's test were performed at a 5% probability for comparison of average. In addition, treatments of the 0 to 0.05 m layer of the soil were also compared to the natural closed area, through the conventional chemical and physical properties and characteristics of its nanoparticles and nanostructures. For these analyze the remaining Cerrado soil was included for comparison with the treatments studied. As nanoparticles (<200 nm) were extracted and characterized by transmission electron microscopy (TEM) and infrared spectrometry (FTIR). The results were evaluated by principal component analysis and hierarchical groupings. Cover crops and mechanical chiseling did not influence the yield of “dryland” rice and “winter” common bean after two years of cultivation. The study of the nanoparticles and nanostructures was sensitive to the changes promoted using mechanical chiseling and the cover crops, thus presenting potential to be a supplementary soil quality indicator tool. The phosphorus (P) was the chemical attribute most influenced by management practices by succession with pearl millet (Pennisetum glaucum) without mechanical chiseling in the two superficial layers and in the other layers by the succession Urochloa ruziziensis (Syn. Brachiaria ruziziensis).The physical and chemical attributes of the soil combined with the characterization of nanoparticles allowed to identify that pearl millet without mechanical chiseling as stable changes to the maintenance of NTS. The geometric and chemical characteristics of the nanoparticles assist in the identification of changes caused by the management practices on the physical and chemical indicators of soil quality. The contribution of cover crops to NTS maintenance is directly linked by the addition of soil organic matter (SOM). Thus, contributing to the improvements of the chemical and physical attributes of soil and influenced the behavior of the nanoparticles and the nanostructure of the soil. / Projeto CNPq 471052/2013-2