The health of the Baltic Sea is negatively affected by hazardous substances such as metals and persistent organic pollutants (POPs), which include legacy pollutants that were banned decades ago, but still circulate in the ecosystem. Elevated levels of legacy pollutants, identified by HELCOM as key hazardous substances, have been found in accumulations of fibrous sediments, so-called fiberbanks and fiber-rich sediments, which derive from old pulp mills along the Swedish north coast. The fiberbanks are deposited in shallow water and bathymetrical models show evidence of their erosion, potentially caused by propeller wash, submarine landslides and gas ebullition. This thesis addresses the potential dispersal of key substances from three fiberbank sites located in a non-tidal Swedish estuary, in which metals and POPs are present in concentrations that may pose a risk for benthic organisms. Metals and POPs are partitioned to organic material and, as expected, show the highest partitioning coefficients (KD) in fiberbanks that have higher TOC levels compared to adjacent areas with fiber-rich sediments (natural clay sediments mixed up with fibers) or relatively unaffected postglacial clays. However, many analytes were found to be present in quantifiable concentrations in pore water, which indicates diffusion of substances from the solid phase to the aqueous phase. To assess the dispersive influence of an abrupt erosional event on dispersion, metals were measured in undisturbed bottom water and in bottom water disturbed by artificial re-suspension of fibrous sediments. The bioavailable, dissolved fraction of metals decreased in bottom water after re-suspension, probably due to the particle concentration effect. In contrast, the total concentrations of metals and number of quantifiable metals increased with particle concentration caused by re-suspension. At one station, the total concentration of chromium (Cr) was elevated to a level where it may lower the ecological status of the water body during periods of substantial erosion (e.g. spring floods or submarine landslides). Analyses of disturbed bottom water revealed, however, that minerogenic particles were preferentially re-suspended compared to organic. This suggests that physical erosion and re-suspension of fiberbank sediments might have a larger effect on dispersal of metals than on POPs. / TREASURE

Submitted by Biblioteca de Pós-Graduação em Geoquímica BGQ (bgq@ndc.uff.br) on 2017-03-24T17:02:56Z No. of bitstreams: 1 dissertacao mestrado.pdf: 2715734 bytes, checksum: f14542bfbb505b150814a53922bc4aac (MD5) / Made available in DSpace on 2017-03-24T17:02:56Z (GMT). No. of bitstreams: 1 dissertacao mestrado.pdf: 2715734 bytes, checksum: f14542bfbb505b150814a53922bc4aac (MD5) / Conselho Nacional de Desenvolvimento Científico e Tecnológico / Universidade Federal Fluminense. Instituto de Química. Programa de Pós-Graduação em Geociências- Geoquímica Ambiental. Niterói, RJ / O estudo da mineralização da matéria orgânica em sedimentos marinhos tem sido investigado em vários locais do mundo a décadas, principalmente devido a grande influência deste processo na mudança das concentrações de nutrientes e metais (Fe, Mn, V, Cd, Cu, Ni, Zn, Ba) dissolvidos na água intersticial nestes ambientes. Assim, a liberação de espécies dissolvidas na água intersticial pode favorecer a disponibilidade das mesmas para a coluna d’água. No entanto, poucos são os estudos que quantificaram as concentrações destas espécies dissolvidas na água intersticial de sedimentos marinhos da costa brasileira. As determinações de COT, TA, C/N, δ13C e perfil granulométrico foram realizadas em testemunhos (curtos e longos) em 3 pontos (P01, P09 e P15) da região de Cabo Frio a fim de caracterizar o sedimento presente na área de estudo. Os resultados mostraram uma predominância de material de origem marinha em todos os pontos e uma semelhança entre os perfis encontrados no P01 e P15. As determinações de Mn e Fe dissolvidos na água intersticial mostraram a presença de zonas de degradação da matéria orgânica dentro da coluna sedimentar por processos de redução de Mn(IV) e Fe(III), respectivamente, em todos os pontos. No entanto, apenas no testemunho longo do ponto P09 (onde foram encontrados os maiores valores de COT, silte e teor de água) foi identificado processo de redução de SO42-, evidenciado por altas concentrações de S2- dissolvido. A redução das concentrações de Fe bem como as concentrações de Cu abaixo do limite de detecção neste perfil indica precipitação de sulfetos estáveis. As concentrações de Ni abaixo do limite de detecção também neste perfil sugerem que este metal pode estar co-precipitando com sulfetos de Fe. As baixas concentrações de Ba dissolvido nesta zona de redução do SO42- indicam que este não ocorre dissolução de barita durante este processo, sugerindo que a atividade sulfato redutora não é muito intensa. De uma forma geral, foram identificados aumentos nas concentrações de PO43-, Cd, Cu, Ni e Zn nas zonas de redução do Fe, indicando processos de desorção de óxidos e hidróxidos de Fe e mineralização da matéria orgânica. O aumento das concentrações de V nestas zonas de degradação em todos os pontos mostraram relação deste metal com mineralização da matéria orgânica. / The study of mineralization of organic matter in marine sediments has been investigated in several locations around the world for decades, mainly due to the great influence of this process of the change concentrations both nutrients and metals (Fe, Mn, V, Cd, Cu, Ni, Zn , Ba) dissolved in pore water of these environments. Thus, the release of dissolved species in the interstitial water can favor the availability for water column. However, few studies have quantified the concentrations of these dissolved species in interstitial water of marine sediments of the brazilian coast. Measurements of TOC, TA, C/N, δ13C and grain size were done on cores (short and long) in 3 points (P01, P09 and P15) in the region of Cabo Frio to characterize the sediment present in the study area. The results showed a predominance of material of marine origin at all points and similarity between the profiles found at P01 and P15. The determinations of Mn and Fe dissolved in the pore water showed the presence of zones of organic matter degradation within the sedimentary column by reduction processes of Mn (IV) and Fe (III), respectively, at all points. However, only the long core of point P09 (where were found the highest values of TOC, silt and TA) was identified process of reduction of SO42-, as evidenced by high concentrations of S2- dissolved. The reduction of Fe concentration, as the concentrations of Cu below of the detection limit in this profile indicates precipitation of sulfides stable. The concentration of Ni below the limit of the detection, also in this profile, suggest that this metal can be co-precipitating with sulfides Fe. The low concentrations of Ba dissolved in reduction zone of SO42-indicate that this does not occur dissolution of barite during this process of organic matter oxidation, suggesting that the activity sulfate reductive is not intense. The increases in concentrations of PO43-, Cd, Cu, Ni and Zn were identified in zones reduction of Fe, indicating processes desorption of oxides and hydroxides of Fe and mineralization of organic matter. The increases concentrations of V in zones of degradation at all points showed relationship of this metal with mineralization of organic matter.

O Complexo Billings é o maior reservatório de água da Região Metropolitana de São Paulo. Devido a sua importância estratégica e à degradação da qualidade de suas águas e sedimentos, a represa foi e continua sendo alvo de muitas pesquisas. No entanto, os valores-guia da qualidade de sedimentos (VGQS) adotados pelas normas nacionais vigentes, usualmente aplicados nestes estudos, baseiam-se na abordagem canadense Threshold Effect Level/Probable Effect Level (TEL/PEL), e sua interpretação quanto aos efeitos tóxicos podem divergir dos países que as originaram. O objetivo deste trabalho foi avaliar o potencial tóxico de contaminantes orgânicos e inorgânicos na água e nos sedimentos do reservatório Billings por meio da utilização de diferentes VGQS empíricos e teóricos e ensaios ecotoxicológicos. Uma abordagem multi-tarefas foi conduzida através de avaliações em campo e em laboratório envolvendo extensas caracterizações químicas, físicas e toxicológicas ao longo de dez pontos do reservatório. Em cada local, os parâmetros de qualidade da água superficial foram monitorados in situ. Amostras de sedimento integral, água intersticial e superficial foram coletadas para a avaliação das propriedades físicas e químicas nestes locais, como granulometria e carbono orgânico total (COT). Os teores de sulfetos volatilizáveis por acidificação (SVA) e os metais extraídos simultaneamente (MES) foram obtidos nas amostras de sedimento integral, assim como as concentrações totais de metais (Cd, Cr, Cu, Fe, Mn, Ni, Pb e Zn) e contaminantes orgânicos (pesticidas organoclorados e hidrocarbonetos aromáticos polinucleares). Os contaminantes foram então comparados a diferentes linhas de evidências (LDE), dentre elas VGQS empíricos (TEL/PEL, LEL/SEL e VRR), VGQS baseados na teoria do Equilíbrio de Partição (EqP) e ensaios ecotoxicológicos com as espécies Daphnia magna e Hyalella azteca em água superficial e sedimento integral, respectivamente. As concentrações de metais nas águas superficial e intersticial do reservatório foram relativamente baixas e ausentes de efeitos crônicos ou agudos pelos ensaios ecotoxicológicos. Os teores de SVA foram superiores aos de MES quando normatizados pela fração COT. Embora a LDE baseada em EqP tenha sugerido a ausência de toxicidade nos sedimentos do reservatório Billings, a mesma ocorreu nos pontos Braço do Rio Grande e Barragem de Pedreira. Os resultados dos ensaios ecotoxicológicos demonstraram efeitos agudos para Hyalella azteca, com sobrevivência dos organismos de 32,5 ± 6,57% e 45 ± 5,77% nos pontos Braço do Rio Grande e Barragem de Pedreira, respectivamente. Efeitos crônicos também foram observados para a espécie H. azteca em ambos os pontos. Os valores de biomassa individuais dos anfípodas foram afetadas quando comparadas ao Controle (0,072 ± 0,01 mg), com valores de 0,032 ± 0,01 mg e 0,031 ± 0,01 mg no Braço do Rio Grande e Barragem de Pedreira, respectivamente. A utilização dos VGQS empíricos TEL/PEL e os Valores de Referência Regionais demonstraram ser eficazes para predição de efeitos tóxicos, visto que as concentrações dos metais Cu, Cr, Ni, e Zn presentes nos sedimentos superaram o limiar PEL em vários pontos do reservatório, indicando uma alta probabilidade de efeitos adversos à biota, comprovada pelos ensaios ecotoxicológicos. As concentrações dos pesticidas organoclorados mirex e DDT encontram-se acima de TEL, enquanto o DDE, mais persistente, demonstrou uma alta probabilidade de ocorrência de efeitos tóxicos (acima de PEL). Embora o EqP não tenha sido eficaz na predição dos efeitos tóxicos, foi imprescindível para compreender a dinâmica dos metais no reservatório, visto que os elevados teores de sulfetos e COT demonstram ser os responsáveis pelo equilíbrio dos metais neste ambiente. Dessa forma, a combinação de VGQS empíricos e teóricos pode - de maneira não regulatória - ser considerada uma solução efetiva e de baixo-custo para a tomada de decisão sobre locais passivos de contaminação. / The Billings Complex is the largest water-storage facility in the São Paulo Metropolitan Region. Due to its strategic importance and the deterioration in its water quality over time, the Billings reservoir was and remains subject of many researches. However, the sediment quality guidelines (SQGs) adopted in Brazil and usually applied in these studies are based on the Canadian Threshold Effect Level/Probable Effect Level (TEL/PEL) and may not suitably predict ecotoxicological effects. The aim of this study was to evaluate the toxicity of organic and inorganic compounds in the overlying water, pore water and bedded sediments of the Billings reservoir through several SQGs and toxicological tests. A laboratory and field assessment was conducted involving extensive physical, chemical, and toxicological characterizations within ten stations of the Billings reservoir. At each sampling station, water quality parameters (pH, redox, DO, conductivity, turbidity, and temperature) were measured in depth (intervals of 1 meter). Bedded surface sediment, sediment pore water, and overlying water were collected to assess the physical and chemical properties at these sites, such as particle size and total organic carbon (TOC). Sediment samples were analyzed for acid volatile sulfides (AVS) and simultaneously extractable metals (SEM), total metals (Cd, Cr, Cu, Fe, Mn, Ni, Pb, and Zn) and organic contaminants (organochlorine pesticides and semivolatile organic compounds). Empirical (TEL/PEL, RRV, and LEL/SEL) and mechanistic (AVS/SEM) SQGs approaches were applied and compared with 10-d toxicity tests with Daphnia magna and Hyalella azteca for overlying water and bedded sediment, respectively. Metals in the overlying and pore water were at a relatively low concentrations and absent of chronic or acute effects. AVS concentrations was greater then SEM in every station of the reservoir, therefore suggesting the absence of toxicity. However, Hyalella azteca post-exposure survival was affected in both Rio Grande branch and Pedreira Dam stations (32,5 ± 6,57% and 45 ± 5,77%, respectively). Relative growth rates were also affected in both Rio Grande branch and Pedreira Dam stations (0,032 ± 0,01 mg and 0,031 ± 0,01 mg) when compared to Control (0,072 ± 0,01 mg). Empirical (TEL/PEL, RRV, and LEL/SEL) guidelines were more suitable for toxicity prediction. Several stations exhibit metal concentrations for Cu, Cr, Ni, and Zn higher than the Canadian PEL adopted in Brazil. Organic compounds such as mirex and DDT were above TEL. Persistent DDT metabolite p,p\'-DDE were above PEL in both Rio Grande branch and Pedreira Dam stations. Although EqP was not suitable for toxicity prediction, it was important for understanding the role of sulfides and TOC for metal contamination in the reservoir. Therefore, the adoption of both empirically and mechanistic SQGs for sediment quality assessments can provide a more accurate and low cost alternative for sediment management decisions.

Liquefaction is a major challenge in geotechnical engineering in which soil strength and stiffness are compromised due to earthquake activity. Understanding and predicting the behaviour and liquefaction susceptibility of soils under cyclic loading is a critical issue in civil engineering, mining and protective engineering. Numerous earthquake-induced ground failure events (e.g., substantial ground deformation, reduced bearing capacity) or liquefaction in natural fine-grained soils or manmade fine-grained soils (i.e., fine tailings) produced by mining activities have been observed and reported in the literature. Tailings are manmade soils that remain following the extraction of metals and minerals from mined ore in a mine processing plant. Traditionally, such tailings are stored in surface tailings impoundments at the mine’s surface. However, geotechnical and environmental risks and consequences related to conventional tailings impoundments have attracted the attention of the engineering community to develop novel methods of tailings disposal and management to minimize geotechnical and environmental risks. Thus, engineers have introduced and implemented innovative tailings technologies—thickened tailings and paste tailings—as cost-effective means for tailings management in mining operations. As both thickened tailings and paste tailings have lower water content and higher solid content than tailings in conventional impoundments, these tailings may be more resistant to liquefaction. However, it should be noted that the seismic or cyclic behaviour of these thickened and paste tailings, with and without heavy rainfall effects, are not fully understood. There is little technical information or data about the behaviour and liquefaction of thickened and paste tailings under seismic or cyclic loading conditions. The objective of the present PhD research is to investigate the response of layered thickened and paste tailings deposits, with and without heavy rainfall effects, to cyclic loads by conducting shaking table tests. To simulate the field deposition of thickened and paste tailings, tailings were deposited in three thin layers in a flexible laminar shear box (FLSB) attached to the shaking table equipment. A sinusoidal seismic loading at a frequency of 1 Hz and peak horizontal acceleration of 0.13g was applied at the bottom of the layered tailings deposits. Acceleration, displacement and pore water pressure responses to the cyclic loading were monitored at the middle depth of each layer of the tailings deposits. Regarding the acceleration response of these thickened and paste tailings deposits (without the effect of heavy rainfall), there was no difference between the middle of the bottom and middle layers or at the base of the shaking table. However, the acceleration at the middle of the top layer differed from the acceleration at the base of the shaking table. Throughout shaking, the layered tailings deposits (with and without the effect of heavy rainfall) exhibited contraction and dilation responses. The excess pore water pressure ratios of the layered thickened tailings deposit that was not exposed to heavy rainfall prior to shaking were found to exceed 1.0 during shaking. However, for the layered paste tailings deposit that was not exposed to the effect of heavy rainfall prior to shaking, the excess pore water pressure ratios were found to be lower than 0.85 during shaking. This reveals that without the effect of heavy rainfall, the layered thickened tailings deposit was susceptible to liquefaction, whereas the layered paste tailings deposit was resistant to liquefaction during shaking. The excess pore water ratios of the layered thickened and the paste tailings deposits that were exposed to heavy rainfall prior to shaking were found to be lower than 0.8 during shaking. This reveals that with the effect of heavy rainfall, the layered thickened and paste tailings deposits were resistant to liquefaction during shaking. The results and findings of this PhD research thus provide valuable information for the implementation of tailings in earthquake-prone areas.

京都大学 / 0048 / 新制・課程博士 / 博士(工学) / 甲第21737号 / 工博第4554号 / 新制||工||1710(附属図書館) / 京都大学大学院工学研究科社会基盤工学専攻 / (主査)教授 木村 亮, 准教授 肥後 陽介, 准教授 木元 小百合 / 学位規則第4条第1項該当 / Doctor of Philosophy (Engineering) / Kyoto University / DFAM

Electricity generation at nuclear power plants produces a large amount of high-level radioactive waste (HLW) every year, which has long-term detrimental effects on humans and the environment. Other applications of nuclear technology (e.g., medicine, research, nuclear weapons, industry) also produce radioactive waste (e.g., low-level radioactive waste, LLW, Intermediate-level waste, ILW). The potential of deep geological repositories (DGRs) as an option for disposal of radioactive waste (HLW, ILW, LLW) has been examined in several countries, including Bulgaria, Canada, China, Finland, France, Germany, India, Japan, Russia, Spain, Sweden, Switzerland, Ukraine and the United Kingdom and are still under discussion. In Ontario, Canada, DGRs with a multi-barrier system comprised of a sedimentary rock formation (i.e., a natural barrier) and an engineered barrier system (EBS) are currently under consideration. An EBS consists of various components, such as waste containers, buffer, backfill, and tunnel sealing materials, intended to prevent the release of radionuclides. Several engineered barrier materials, including a mixture of bentonite and sand, are currently being considered for use in DGRs for nuclear waste in Ontario. Bentonite has some advantageous physical and chemical properties, such as low permeability, high plasticity, and high swelling potential, which provide it with a good sealing ability and thus make it an effective barrier. However, interaction between the compacted bentonite–sand mixture and underground water chemistry fluids (chemical factor) in the DGR could significantly alter the favourable properties of bentonite (e.g., swelling potential), thus influencing its performance when used in an EBS and eventually jeopardizing the overall safety of DGRs. In addition, other parameters, such as the clay content, initial dry density and moisture content of the compacted barrier (physical factors), as well as the presence of salts in groundwater may affect the physical and physiochemical properties of barrier materials. Moreover, during the lifetime of a DGR for used spent fuel, the bentonite–based barrier material will not only be exposed to a broad range of groundwaters with different chemical compositions, but also to high temperatures (heat generated by the nuclear wastes) (thermal factor). Thus, the interaction between the compacted bentonite–sand mixture, the surrounding groundwater and the heat from the nuclear waste material could jeopardize the favourable properties of the bentonite-based (bentonite-sand) barrier material. Properties of a bentonite-sand barrier is an important characteristic to study while designing and constructing an EBS for a DGR. Thus, to understand and assess the operations of DGRs in Ontario, comprehensive studies must be performed on engineering properties like swelling behaviour, permeability, and thermal conductivity. The goal of this research study is to experimentally investigate the physical, chemical and thermal factors that influencing the engineering properties of a barrier material made up of bentonite-sand composite used in DGRs for nuclear waste in Ontario. Compacted samples are subjected to one-dimensional free swell test to understand the swelling behaviour of the material. Hydraulic conductivity was investigated using a flexible wall permeability test. Thermal conductivity and diffusivity were tested using Decangon KD2 Pro with TR-1 and and KS-1 sensors. The specimens contain different bentonite–sand mixture ratios (20:80, 30:70, 50:50, and 70:30 dry mass), and they are tested under conditions with differing bentonite content, dry density, groundwater chemistry, and temperature. Additional tests were conducted to investigate the microstructure of the specimens. These tests include X-ray diffraction (XRD) analysis, mercury intrusion porosimetry (MIP), and thermogravimetric analyses (TG/DTG). The results reveal that the time and strain required to achieve maximum swelling of compacted bentonite–sand specimens increase with the increase of initial dry density. The simulated saline solutions of Guelph and Trenton groundwater are found to suppress the swelling of the bentonite–sand specimens. This in turn leads to the increase of hydraulic conductivity and decrease of thermal properties of the barrier material. However, the impact of the salinity is significantly reduced by increasing the dry densities and sand content of the compacted material. Moreover, the coupled effect of salinity and temperature decreases the swelling potential of the bentonite-sand mixture. Also, some transformation of Na-montmorillonite into Ca-Montmorillonite was observed. The results also indicate that some montmorillonites might have been transformed into illites, thereby further decreasing the swelling potential of the bentonite-based barrier.

No description available.

In der Arbeit wird gezeigt, wie man die Bodensteifigkeit bei sehr kleinen Dehnungen sowie die Abnahme der Steifigkeit mit zunehmender Scherdehnung in Labor- und Feldversuchen ermitteln kann. Dazu werden typische Eigenschaften mineralischer und organischer Böden einschließlich Korrelationen zusammengestellt und wesentliche Unterschiede zum Bodenverhalten bei großen Dehnungen, insbesondere hinsichtlich der Steifigkeit und der Spannungsabhängigkeit aufgezeigt. Weiterhin wird dargelegt, wie man mit dem hypoplastischen Stoffgesetz mit intergranularen Dehnungen das Bodenverhalten bei kleinen Dehnungen wirklichkeitsnah erfassen kann und wie die Stoffparameter zu bestimmen sind. Für die realistische Erfassung des Bodenverhaltens infolge zyklischer Belastung einschließlich der Ausbildung von Hystereseschleifen wird eine Modifizierung des hypoplastischen Stoffgesetzes unter Einführung eines zusätzlichen Stoffparameters vorgenommen. Es wird gezeigt, wie dieser Parameter in zyklischen Laborversuchen bestimmt werden kann und wie damit die Akkumulation von Dehnungen bei drainierten Bedingungen bzw. von Porenwasserdrücken bei undrainierten Bedingungen zuverlässig prognostiziert werden kann. Anhand der dynamischen Beanspruchung eines Eisenbahndammes auf weichem, organischem Untergrund wird das modifizierte hypoplastische Stoffgesetz mit intergranularen Dehnungen für ein bodendynamisches Randwertproblem angewendet und gezeigt, dass damit das Bodenverhalten realistisch abgebildet werden kann. Die Berechnungsergebnisse zeigen eine gute Übereinstimmung mit Ergebnissen von Schwingungsmessungen und Langzeitverformungsmessungen. Es werden bodendynamische Berechnungen zur Wellenausbreitung sowohl eindimensional als auch im Halbraum mit unterschiedlichen Stoffgesetzen geführt und Vergleiche mit analytischen Lösungen vorgenommen. Dazu wird gezeigt, welche Anforderungen an numerische Berechnungen zur Wellenausbreitung, insbesondere hinsichtlich Wahl der Zeitschritte, Elementgröße bzw. Knotenabstände, Größe des FE-Netzes und Modellierung der FE-Ränder erforderlich sind. / In this thesis it is shown how to determine the soil stiffness at very small strains, as well as the decrease in stiffness with increasing shear strain amplitude in laboratory and field tests. Typical properties and empirical correlations of coarse-, fine-grained and organic soils are collected and significant differences in soil stiffness and stress-dependence at small strains compared to large strains are shown. Further it is shown how one can realistically reproduce the soil behaviour at small strains with the hypoplastic constitutive model with intergranular strains and how the material parameters are determined. For a realistic prediction of soil behaviour due to cyclic loading including hysteresis loops in the stress-strain relationship, a modification of the hypoplastic constitutive model is made by using an additional material parameter. It is shown how this additional parameter can be determined in cyclic laboratory tests and how the accumulation of strains in drained conditions and excess pore pressures built up in undrained conditions can be realistically reproduced. Based on the dynamic load on a railway embankment on soft marshy ground, the modified hypoplastic constitutive model with intergranular strains is applied for a boundary value problem. It is demonstrated, that the soil behaviour can be reproduced realistically. Numerical results show a good agreement with results of vibration measurements and measurements of permanent displacements. A dynamical numerical analysis is performed for both one-dimensional and half-space conditions. Different constitutive models have been applied and compared with analytical solutions. The results demonstrate requirements on numerical analysis of wave propagation, in particular with regards to time steps, element size, node spacing, size of the FE mesh and boundary conditions.

An extensive amount of natural gas trapped in the subsurface is found as methane hydrate. A fundamental understanding of natural hydrate-bearing sediments is required to engineer production strategies and to assess the risks hydrates pose to global climate change and large-scale seafloor destabilization. This thesis reports fundamental studies on hydrate nucleation, morphology and the evolution of unsaturation during dissociation, followed by additional studies on sampling and pressure core testing. Hydrate nucleation is favored on mineral surfaces and it is often triggered by mechanical vibration. Continued hydrate crystal growth within sediments is governed by capillary and skeletal forces; hence, the characteristic particle size d10 and the sediment burial depth determine hydrate morphologies in natural sediments. In aged hydrate-bearing sand, Ostwald ripening leads to patchy hydrate formation; the stiffness approaches to the lower bound at low hydrate saturation and the upper bound at high hydrate saturation. Hydrate saturation and pore habit alter the pore size variability and interconnectivity, and change the water retention curve in hydrate-bearing sediments. The physical properties of hydrate-bearing sediments are determined by the state of stress, porosity, and hydrate saturation. Furthermore, hydrate stability requires sampling, handling, and testing under in situ pressure, temperature, and stress conditions. Therefore, the laboratory characterization of natural hydrate-bearing sediments faces inherent sampling disturbances caused by changes in stress and strain as well as transient pressure and temperature changes that affect hydrate stability. While pressure core technology offers unprecedented opportunities for the study of hydrate-bearing sediments, careful data interpretation must recognize its inherent limitations.

Submitted by Biblioteca de Pós-Graduação em Geoquímica BGQ (bgq@ndc.uff.br) on 2016-03-28T17:23:27Z No. of bitstreams: 1 Dissertação_Christiene_FINAL_.pdf: 2691556 bytes, checksum: 6c071c6fc087c647c3aae5c59f4526d4 (MD5) / Made available in DSpace on 2016-03-28T17:23:27Z (GMT). No. of bitstreams: 1 Dissertação_Christiene_FINAL_.pdf: 2691556 bytes, checksum: 6c071c6fc087c647c3aae5c59f4526d4 (MD5) / Conselho Nacional de Desenvolvimento Científico e Tecnológico / Universidade Federal Fluminense. Instituto de Química. Programa de Pós-Graduação em Geociências-Geoquímica. Niterói, RJ / A diagênese recente de metais-traço redox-sensitivos, nutrientes e produtos metabólicos (Mn, Fe, ΣNO3-, NH4+, PO43-, SO42-, ΣH2S, sílica dissolvida (SiD), e alcalinidade) nas águas intersticiais e os fluxos de ΣNO3-, NH4+, PO43- e SiD na interface água-sedimento (IAS) foram estudados em três ambientes que representam cenários diferentes de aportes antrópicos da zona costeira do estado do Rio de Janeiro, incluindo a Baía de Cabo Frio (CF), a Enseada de Jurujuba (JU) e a Baía de Sepetiba (SE). As razões C:N:P e as assinaturas isotópicas (13C e 15N) dos sedimentos indicaram que a MO é de origem marinha no testemunho CF e JU. Já em SE ocorre matéria orgânica (MO) de origem marinha e terrestre, havendo predominância de origem fitoplanctônica. As concentrações de COT demonstraram similaridades no acúmulo do material orgânico entre a BC e a SE, enquanto JU apresentou concentrações mais altas. Os padrões de distribuição das zonas redox dentro da coluna sedimentar, baseado nos perfis de água intersticial, nos ambientes estudados mostraram serem influenciados pela variabilidade do teor de COT e processos de bioturbação e/ou físicos. Na CF, sob condições subóxicas, as principais reações redox foram bem identificadas nos sedimentos superficiais e seguiu a sequência teórica do consumo oxidante: ΣNO3->MnO2>Fe(OH)3, a zona de redução de SO42- não foi evidenciada nesse perfil. Na JU, sob condições anóxicas, os perfis de água intersticial indicaram um zoneamento redox “comprimido”, favorecendo a contração das zonas óxica-subóxica e expansão da região sulfídrica. As altas concentrações de alcalinidade, amônio e sulfeto indicaram degradação intensiva de matéria orgânica no testemunho JU, dominado pela zona de redução de sulfato e uma influência menor pela das reduções de ΣNO3-, MnO2 e Fe(OH)3. Na SE, sob condições subóxicas e a presença de macrofauna observada no sedimento, duas sequências diagenéticas sobrepostas foram observadas. A primeira sequência envolveu a redução do NO3-, MnO2 e Fe(OH)3. A segunda sequência diagenética envolveu a redução do MnO2 e Fe(OH)3. A presença de duas sequências diagenéticas pode estar relacionada aos efeitos de bioturbação e/ou outras perturbações físicas, como eventos de dragagem em áreas adjacentes e atividades de embarcações que causam ressuspensão do sedimento. A ocorrência de variação da concentração de COT no topo do testemunho SE, ressalta a perturbação do sedimento. Foi evidenciado que os fluxos de NO3- e NH4+ em CF são influenciados pelos processos de desnitrificação, em JU pelo processo de desnitrificação e redução desassimilatória de nitrato para amônio, já em SE pelos processos de desnitrificação e nitrificação. O fluxo do PO43- foi afetado pela precipitação de mineral autigênico e bioturbação do sedimento. E o fluxo de SiD foi afetado pela gradual dissolução de sílica biogênica com o aumento da profundidade. Em JU foram observados os maiores fluxos de NO3-, NH4+ e SiD na IAS. No entanto, o fluxo de PO43- mais alto foi observado na IAS da Baía de Sepetiba, provavelmente devido às baixas concentrações de PO43- encontradas na água de fundo em relação às outras áreas de estudo / The early diagenesis of the redox-sensitive trace metals, nutrients, metabolic products (Mn, Fe, ΣNO3-, NH4+, PO43-, SiD, SO42-, H2S and alcalinity) in pore waters and the fluxes of the ΣNO3-, NH4+, PO43- and DSi at the sediment-water interface (SWI) were studied in three environments that represent different scenarios of anthropogenic inputs of the coastal zone of the state of Rio de Janeiro, including the Cabo Frio Bay (CF), Jurujuba Sound (JU) and Sepetiba Bay (SE). The C:N:P ratios and isotopic signatures (13C and 15N) of the sediments indicated that organic matter (OM) is of marine origin in CF and JU core. In SE occurs OM marine and terrestrial origin, with predominance of phytoplankton origin. The TOC concentrations have demonstrated similarities in the accumulation of organic material between BC and SE, while JU submitted higher concentrations. The distribution patterns of redox zones within the sedimentary column, based on pore water profiles, in the studied environments showed to be influenced by the variability of the TOC content and bioturbation and/or physical processes. In CF, under suboxic conditions, the main redox reactions have been identified in surface sediments and followed the theoretical result of oxidant consumption: ΣNO3-> MnO2> Fe (OH)3, the SO42- reduction zone was no evidence in this profile. In JU, under anoxic conditions, the pore water profiles indicated a redox zone ‘compressed’, favoring the contraction of the oxic-suboxic zones and expansion of sulfidic region. The high concentrations of alkalinity, ammonium and sulfide indicated intensive degradation of OM in JU core dominated by the sulfate reduction zone and a smaller influence by the ΣNO3-, MnO2 and Fe (OH)3 reductions. In SE, under suboxic conditions and with the observed presence of macrofauna in the sediment, two overlapped diagenetic sequences can be observed. The first sequence involved the reduction of ΣNO3-, MnO2 and Fe (OH)3. The second diagenetic sequence involved the reduction of MnO2 and Fe (OH)3. The presence of two diagenetic sequences may be related to effects bioturbation and/or other physical disturbances, such as dredging events in adjacent areas and craft activities that cause sediment resuspension. The occurrence of variation of TOC concentration at the top of the SE core, emphasizes the disturbance of sediment. It was evidenced that the fluxes of ΣNO3- and NH4+ in CF are influenced by denitrification processes, in the JU by process denitrification and nitrate dissimilatory reduction to ammonium, as in SE by nitrification and denitrification processes. The PO43- fluxes was affected by the precipitation of autigenic mineral and bioturbation of the sediment. And the SiD flux is affected by the gradual dissolution of biogenic silica with increasing depth. In JU were observed larger fluxes of ΣNO3-, NH4+ and DSi at the SWI were observed. However, the higher PO43- fluxes was observed at the SWI Sepetiba Bay, probably due to low concentrations of PO43- found in the overlying water in relation to other areas of study.