Olivine is the most abundant mineral in Earth's upper mantle and is one of the major minerals discovered in extraterrestrial objects. Its physical properties govern the dynamics of the upper mantle. The most dynamic regions of the upper mantle are sites where melting and melt segregation occurs. These regions are also the most variable in terms of their oxygen fugacity. We therefore conducted piston cylinder experiments to determine the intergranular melt distribution, and explore a range of oxygen buffers. We annealed olivine aggregates in metallic and graphite capsules to determine the oxygen fugacities set by the capsule materials. These experiments show that oxygen fugacities are below their corresponding metal-oxide buffers. The oxygen fugacity in nickel80-iron20 and graphite capsules most closely represents the intrinsic oxygen fugacity of Fo90 olivine, while iron capsules are too reducing perhaps explaining the formation of "dusty" olivine in chondrites. We annealed olivine-basalt aggregates in order to determine the melt distribution. The results show that the length of olivine grain boundaries wetted by melt (grain boundary wetness) increases with increasing melt content to values well above those predicted by a simplified model which is commonly applied to this system. At fixed melt content the grain boundary wetness increases with increasing grain size. These observations emphasize that the dihedral angle of the simplified system is not adequate to characterize the melt distribution in partially molten rocks. Our observations indicate that at upper mantle grain sizes the shear viscosity of partially molten rocks is one order of magnitude lower than predicted by the simplified model. Naturally partially molten rocks exist in the form of olivine-rich troctolites or plagioclase dunites, but the conditions for their formation are not entirely clear. We therefore conducted step-cooling experiments that indicate that slow cooling of samples with a steady-state microstructure reproduces the interstitial geometry observed in natural samples. The grain boundary wetness determined from the interstitial phases is somewhat reduced during slow cooling relative to samples quenched from high temperature. The microstructural similarity of experimental and natural samples suggests that mush zones identified beneath mid-ocean ridges may have lower melt contents than previously envisioned. / 2016-11-18T00:00:00Z

No description available.

No description available.

This thesis is concerned with the numerical simulation of mixtures of chemically reacting fluids at high pressures. Mixture rules are established, accommodating components that do not follow the thermally perfect Equation of State (EoS), and including formulas for the fugacities. Particular attention has been given to the species EoS originally developed by Hirschfelder, Buehler, McGee and Sutton. The Law of Mass Action that governs chemical equilibrium of mixtures of fluids is presented. The common assumption of neglecting fugacities contributions when calculating the equilibrium composition is assessed by comparing complete thermochemical predictions with those obtained by reduced models. For air mixtures at high pressures and moderate temperatures, species thermally imperfect EoS effects are significant. However, the contribution of fugacities to the Law of Mass Action is found to be small, at least for mixtures of super-critical dissociating gases. Similar conclusions apply to combustion mixtures (involving hydrogen and oxygen).

No description available.

<p>Persistent organic pollutants (POPs) is a group of chemicals that are toxic, undergo long-range transport and accumulate in biota. Due to their persistency the distribution and recirculation in the environment often continues for a long period of time. Thereby they appear virtually everywhere within the biosphere, and poses a toxic stress to living organisms. In this thesis, attempts are made to contribute to the understanding of factors that influence the distribution of POPs with focus on processes in the marine environment. The bioavailability and the spatial distribution are central topics for the environmental risk management of POPs. In order to study these topics, various field studies were undertaken. To determine the bioavailable fraction of polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs), polychlorinated naphthalenes (PCNs), and polychlorinated biphenyls (PCBs) the aqueous dissolved phase were sampled and analysed. In the same samples, we also measured how much of these POPs were associated with suspended particles. Different models, which predicted the phase distribution of these POPs, were then evaluated. It was found that important water characteristics, which influenced the solid-water phase distribution of POPs, were particulate organic matter (POM), particulate soot (PSC), and dissolved organic matter (DOM). The bioavailable dissolved POP-phase in the water was lower when these sorbing phases were present. Furthermore, sediments were sampled and the spatial distribution of the POPs was examined. The results showed that the concentration of PCDD/Fs, and PCNs were better described using PSC- than using POM-content of the sediment. In parallel with these field studies, we synthesized knowledge of the processes affecting the distribution of POPs in a multimedia mass balance model. This model predicted concentrations of PCDD/Fs throughout our study area, the Grenlandsfjords in Norway, within factors of ten. This makes the model capable to validate the effect of suitable remedial actions in order to decrease the exposure of these POPs to biota in the Grenlandsfjords which was the aim of the project. Also, to evaluate the influence of eutrophication on the marine occurrence PCB data from the US Musselwatch and Benthic Surveillance Programs are examined in this thesis. The dry weight based concentrations of PCB in bivalves were found to correlate positively to the organic matter content of nearby sediments, and organic matter based concentrations of PCB in sediments were negatively correlated to the organic matter content of the sediment.</p>

La thèse est basée sur une étude pétrologique et géochimique de xénolites mantelliques provenant du centre du craton sibérien et de l’Asie centrale entre le lac Baïkal et la Mongolie. Le but est d’établir l'état redox du manteau lithosphérique continental dans ces deux domaines géodynamiques distincts (ancien craton, ceinture mobile phanérozoïque) et mettre la fugacité d’oxygène en relation avec le régime thermique et la spéciation des fluides C-O-H. Les fugacités d’oxygène sont calculées sur la base des rapports Fe2+/Fe3+ dans les minéraux (spinelles et grenats) de péridotites, obtenus par spectrométrie Mössbauer. En détail, l’étude porte sur : (i) les microstructures et la composition minéralogique et chimique des xénolites ; (ii) les rapports Fe2+/Fe3+ dans les minéraux par spectrométrie Mössbauer; (iii) les températures et pressions d’équilibration des xénolites; (iv) la fugacité d’oxygène à partir des compositions des minéraux; (v) la spéciation des fluides C-O-H coexistant avec les roches mantelliques. Les résultats supportent les trois conclusions majeures. (1) La fugacité d’oxygène dans le manteau Iithosphérique au centre du craton sibérien décroît de +1 à -4 ΔlogʄO2 (FMQ) entre 70 et 220 km, accompagnée de variations latérales significatives. (2) L’état redox du manteau lithosphérique en Asie centrale est très hétérogène avec une décroissance importante lors de la transition spinelle-grenat de +0 à -3 ΔlogʄO2 (FMQ) à 50-90 km. (3) La spéciation des fluides C-O-H évolue avec la profondeur depuis H2O-CO2 en haut du manteau vers H2O-CH4 à la limite lithosphère-asthénosphère, indépendamment du profil thermique et de l’épaisseur de la lithosphère / The thesis is based on a petrologic and geochemical study of mantle xenoliths from the central Siberian craton and the Baikal-Mongolia region of central Asia. Its goal is to establish the redox regime of the lithospheric mantle in these two domains with distinct tectonic settings and age and relate it to thermal regime and the speciation of C-0-H fluids. Oxygen fugacity is calculated based on Fe2+/Fe3+ ratios in spinel and garnet of mantle peridotites obtained by Mössbauer spectroscopy. The study deals with the following topics: (i) microstructures, chemical and mineralogical composition of the xenoliths; (ii) Fe2+/Fe3+ ratios in minerals by Mössbauer spectroscopy; (iii) equilibration temperatures and pressures using mineral thermo-barometry; (iv) oxygen fugacity from mineral compositions using oxybarometry; (v) proportions of molecular components in C-0-H fluids coexisting with the studied rocks. The three main conclusions of this study are: (1) Oxygen fugacity in the lithospheric mantle in the central Siberian craton decreases from +1 to -4 ΔlogʄO2 (FMQ) at depths from 70 to 220 km and shows significant lateral variations. (2) The lithospheric mantle beneath the Baikal-Mongolia region shows important redox heterogeneities, with a sharp decrease in oxygen fugacity (from +0 to -3 AlogfO2 (FMQ)) during the transition from the spine! to garnet facies peridotites at 50 to 90 km. (3) The speciation of C-O-H fluids changes with depth from essentially H2O-CO2 in the shallow lithospheric mantle to H2O-CH4 at the lithosphere-asthenosphere boundary regardless of the thermal state and the thickness of the lithosphere

Temperature (T), Pressure (P) and Oxygen fugacity (fO2) conditions were established for the Três Ranchos IV (diamond-bearing) and Limeira I (sterile) kimberlites of the Coromandel-Três Ranchos kimberlite field (Minas Gerais and Goiás, Brazil), Alto Paranaíba Alkaline Province (APAP), in order to draw a possible correlation between these intensive crystallization parameters and diamond instability. Both Três Ranchos IV and Limeira I are classified as coherent macrocrystic kimberlites, with an inequigranular texture formed by partially-to-fully altered olivine, phlogopite megacrysts up to 1 cm wide, macrocrysts (0.5-10 mm-sized), and crustal xenoliths set in a very fine groundmass composed mainly by perovskite, olivine, phlogopite, spinel, serpentine and carbonates identified in both intrusions. Apatite, ilmenite and monticellite are also present, but only in LM-I. Garnet macrocrysts and centimetric pyroxene xenocrysts phases are also present in Três Ranchos IV and Limeira I, respectively. The samples, strongly enriched in incompatible elements, are all MgO-rich, with high Mg# content. In order to apply different geotherm-and-oxybarometers in the calculation of P-T-fO2 conditions and to characterize the compositional variation of TR-IV and LM-I kimberlites, major, minor and trace-element concentrations of the main mineral phases were obtained by electron microprobe and LA-ICP-MS. Olivine cores of Limeira I present higher NiO, CaO and lower Cr2O3 contents than those from Três Ranchos IV. Mg# [(Mg/Mg+FeT), mol.%) ranges from 87 to 92 mol.% in TR-IV and from 83 to 92 mol.% in LM-I. The trace-element contents of olivine are similar in both kimberlites, the concentrations of Li, Zn and Mn appearing to be higher at olivine rims. In olivines from both intrusions, a pattern of enrichment in Zr, Ga, Nb, Sc, V, P, Al, Ti, Cr, Ca, and Mn in rims regions, is observed in the \"melt trend\" whereas enrichment in Zn, Co, Ni and possibly Na in cores regions, is found in the \"mantle trend.\" In monticellite specimens from Limeira I, Mg# ranges from 72 to 93.8, while Ca/(Ca+Mg) ratios range from 35 to 58 mol.%. The perovskite composition in both LM-I and TR-IV remains close to the ideal CaTiO3, perovskite, but a variation from core endmembers (average Lop16 and Prv78) towards the rims (average Lop13 and Prv81) can be noticed in TR-IV samples. The highest concentrations of light rare earth elements (LREE), Nb, and Fe3+ are also observed in perovskites from the TR-IV kimberlite. Macrocrystic spinels of TR-IV kimberlite are Al-rich, whereas the groundmass crystals range from magnesiochromite to chromite. Ilmenites from LM-I are characterized by high MgO values at a given TiO2, with a large variation in Cr2O3. Pyrope garnets (62 to 73 mol.%) are present only in TR-IV, with Mg# ranging from 72 to 79 mol.%, being classified as lherzolitic (G9) and pyroxenitic (G4, G5). Diopside occurs as xenocrysts in LM-I and as microphenocrysts in TR-IV, with Mg# ranging from 85 to 91 and from 87 to 92, respectively. Xenocrystic diopsides from LM-I present higher MgO and FeO concentrations with monticellite grains along crystal rims and fractures. Temperature estimates for the LM-I kimberlite, obtained from the composition of diopside xenocrysts and Al-in olivine concentrations, ranging from 718 to 985 °C. Pressure ranges from 34 to 47 Kbar, as calculated using an empirical curve from a 37-mW/m2 geotherm proposed in the literature for Alto Paranaíba magmas. For TR-IV, temperature values ranging from 975 to 1270°C were obtained from Al-in olivine and Ni-in garnet concentrations. Pressures in the range from 18 to 34 Kbar were obtained from major element composition of garnet samples from TR-IV kimberlite. The fO2 of the TR-IV constrained by perovskite (kimberlite cognate phase) oxygen barometry ranges from NNO-7 to NNO+4, while for LM-I values range from NNO+6 to NNO-4. For the LM-I intrusion, monticellite, another cognate phase used as an oxybarometer, yielded a value range of NNO-4 to NNO+2. A change in the oxygen fugacity from cores towards rim recorded in the perovskites and the monticellite crystals is also noticed. The oxygen fugacity estimates of this work are the first ever calculated for magmas of the Alto Paranaíba Alkaline Province. All P-T-fO2 values obtained are consistent with literature data on the APAP. Clinopyroxene xenocrysts from LM-I were classified as garnet-facies clinopyroxene, according to the compositions obtained in this work. Such results, along with pressure, and temperature data from and the presence of Mg-ilmenite in LM-I (known to be sterile), indicate that the kimberlite magma might have at least crossed the diamond stability field. The variation in oxygen fugacity observed in both kimberlites possibly reflects the instability of diamonds in these magmas since LM-I presents slightly higher oxidation conditions. / Foram estabelecidas as condições de fugacidade de temperatura (T), pressão (P) e fugacidade de oxigênio (fO2) para os kimberlitos Três Ranchos IV (diamantífero) e Limeira I (LM-I, estéril) do supercampo kimberlítico Coromandel-Três Ranchos (Minas Gerais e Goiás, Brasil), da província alcalina Alto Paranaíba (APAP), com o intutito de determinar uma possível correlação entre tais parâmetros intensivos de cristalização e a instabilidade de diamante daqueles magmas. As intrusões Três Ranchos IV e Limeira I foram classificados como kimberlitos macrocrísticos coerentes, com textura inequigranular evidenciada por megacristais de olivina de até 1 cm parcialmente alterados, macrocristais de flogopita (0.5-10 mm) e xenólitos crustais dispostos em uma matriz muito fina composta principalmente por perovskita, olivina, flogopita, espinélio, serpentina e carbonatos em ambas as intrusões, com adição de apatita, ilmenita e monticelita apenas em LM-I. Macrocristais de granada e xenocristais centimétricos de piroxênio e também são fases minerais presentes em Três Ranchos IV e Limeira I, respectivamente. As amostras são todas ricas em MgO, com alto teor de Mg# e são fortemente enriquecidas em elementos incompatíveis. Concentrações de elementos maiores, menores e traços das principais fases minerais foram obtidas por análises de Microssonda Eletrônica e LA-ICP-MS, com o objetivo de aplicar diferentes geotermo-e-oxibarômetros no cálculo das condições de P-T-fO2 e caracterizar a variação composicional dos kimberlitos TR-IV e LM-I. Núcleos de olivina de Limeira I apresentam maiores teores de NiO, CaO e menores teores de Cr2O3 que os dos cristais de olivina de Três Ranchos IV. O Mg# [(Mg/Mg+FeT), em prop.mol.] calculado a partir das olivinas analisadas varia de 87 a 92 mol.% para TR-IV e de 83 a 92 mol.% para LM-I. O conteúdo de elementos-traço da olivina é semelhante para ambos os kimberlitos, sendo que as concentrações de Li, Zn e Mn parecem ser maiores nas bordas dos cristais de olivina. Nas olivinas das duas intrusões, foram observados tanto um padrão de enriquecimento em Zr, Ga, Nb, Sc, V, P, Al, Ti, Cr, Ca e Mn nas porções de borda, característico do \"melt trend\", quanto um enriquecimento em Zn, Co, Ni e possivelmente Na nas porções de núcleo, notável no \"mantle trend\". Os cristais de monticelita de LM-I apresentam Mg # variando de 72 a 93.8 mol.%, com o índice Ca/(Ca + Mg) variando entre 35-58 mol%. A composição dos cristais de perovskita de LM-I e TR-IV analisados permanece próxima do ideal CaTiO3, mas é notável uma variação dos membros finais dos núcleos (Lop16 e Prv78 médios) às bordas (Lop13 e Prv81 médios) nas amostras de TRIV. As maiores concentrações de elementos terras raras leves (ETRL), Nb e Fe3+ também são observadas nas perovskitas de TR-IV. Os macrocristais de espinélios em amostras de TR-IV são ricos em Al, enquanto os cristais da matriz variam de magnesiocromita a cromita. Cristais de ilmenita são identificados somente em LM-I, sendo caracterizados pelo alto teor de MgO, com grande variação nas concentrações de Cr2O3. As granadas são tipo piropo (62 a 73 mol.%) e estão presentes apenas em TR-IV, com Mg# variando de 72 a 79 mol.%, classificadas como lherzolíticas (G9) e piroxeníticas (G4, G5). O diopsídio ocorre como xenocristais em LM-I e como microfenocristais em TR-IV, com Mg# variando de 85 a 91 mol.% e de 87 a 92 mol.%, respectivamente. Os xenocristais de diopsídio presentes em LM-I apresentam maior concentração de MgO e FeO e são envoltos por coroa de monticelita. As estimativas de temperatura do kimberlito LM-I foram obtidas utilizando as composições dos xenocristais de diopsídio e as concentrações de Al presentes em cristais de olivina, resultando em um intervalo entre 718 e 985 °C. Enquanto que a pressão varia de 34 a 47 Kbar e foi calculada utilizando uma curva empírica de uma geoterma de 37 mW/m2 proposta na literatura para magmas da Província Alcalina do Alto Paranaíba. Para TR-IV foram obtidas temperaturas a partir das concentrações de Al em olivina e de Ni em granada, variando de 975 a 1270 °C. O intervalo de pressão de 18 a 34 Kbar foi obtido a partir da composição dos principais elementos em granada amostrada de TR-IV. A fugacidade de oxigênio registrada em perovskitas (fase cognata de kimberlito) de TR-IV varia de NNO-7 a NNO + 4, e de NNO + 6 a NNO-4 em LM-I. A monticelita, outra fase cognata, também foi utilizada como oxibarômetro, resultando em um intervalo de NNO-4 a NNO + 2 para a intrusão LM-I, onde está presente. Também é notável uma mudança na fugacidade de oxigênio dos núcleos para a borda em perovskitas e em cristais de monticelita. As estimativas de fO2 obtidas neste trabalho foram as primeiras calculadas para magmas da província alcalina do Alto Paranaíba. Todos os resultados de P-T-fO2 obtidos são consistentes com dados da APAP reportados na literatura. Os xenocristais de clinopiroxênio em LM-I foram classificados como clinopiroxênio de fácies granada de acordo com as composições obtidas neste trabalho. Essa informação, juntamente com os dados de pressão e temperatura, além da presença de Mg-ilmenita em LMI (conhecido por ser estéril), indica que este magma kimberlítico pode ter ao menos cruzado o campo de estabilidade do diamante, e que é possível que a variação na fugacidade de oxigênio observada em ambos TR-IV e LM-I pode ter-se refletido na instabilidade destes xenocristais nestes magmas, uma vez que Limeira I apresenta condições de oxidação levemente mais altas.

Persistent organic pollutants (POPs) is a group of chemicals that are toxic, undergo long-range transport and accumulate in biota. Due to their persistency the distribution and recirculation in the environment often continues for a long period of time. Thereby they appear virtually everywhere within the biosphere, and poses a toxic stress to living organisms. In this thesis, attempts are made to contribute to the understanding of factors that influence the distribution of POPs with focus on processes in the marine environment. The bioavailability and the spatial distribution are central topics for the environmental risk management of POPs. In order to study these topics, various field studies were undertaken. To determine the bioavailable fraction of polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs), polychlorinated naphthalenes (PCNs), and polychlorinated biphenyls (PCBs) the aqueous dissolved phase were sampled and analysed. In the same samples, we also measured how much of these POPs were associated with suspended particles. Different models, which predicted the phase distribution of these POPs, were then evaluated. It was found that important water characteristics, which influenced the solid-water phase distribution of POPs, were particulate organic matter (POM), particulate soot (PSC), and dissolved organic matter (DOM). The bioavailable dissolved POP-phase in the water was lower when these sorbing phases were present. Furthermore, sediments were sampled and the spatial distribution of the POPs was examined. The results showed that the concentration of PCDD/Fs, and PCNs were better described using PSC- than using POM-content of the sediment. In parallel with these field studies, we synthesized knowledge of the processes affecting the distribution of POPs in a multimedia mass balance model. This model predicted concentrations of PCDD/Fs throughout our study area, the Grenlandsfjords in Norway, within factors of ten. This makes the model capable to validate the effect of suitable remedial actions in order to decrease the exposure of these POPs to biota in the Grenlandsfjords which was the aim of the project. Also, to evaluate the influence of eutrophication on the marine occurrence PCB data from the US Musselwatch and Benthic Surveillance Programs are examined in this thesis. The dry weight based concentrations of PCB in bivalves were found to correlate positively to the organic matter content of nearby sediments, and organic matter based concentrations of PCB in sediments were negatively correlated to the organic matter content of the sediment.

The thesis is based on a petrologic and geochemical study of mantle xenoliths from the central Siberian craton and the Baikal-Mongolia region of central Asia. Its goal is to establish the redox regime of the lithospheric mantle in these two domains with distinct tectonic settings and age and relate it to thermal regime and the speciation of C-0-H fluids. Oxygen fugacity is calculated based on Fe2+/Fe3+ ratios in spinel and garnet of mantle peridotites obtained by Mössbauer spectroscopy. The study deals with the following topics: (i) microstructures, chemical and mineralogical composition of the xenoliths; (ii) Fe2+/Fe3+ ratios in minerals by Mössbauer spectroscopy; (iii) equilibration temperatures and pressures using mineral thermo-barometry; (iv) oxygen fugacity from mineral compositions using oxybarometry; (v) proportions of molecular components in C-0-H fluids coexisting with the studied rocks. The three main conclusions of this study are: (1) Oxygen fugacity in the lithospheric mantle in the central Siberian craton decreases from +1 to -4 ΔlogʄO2 (FMQ) at depths from 70 to 220 km and shows significant lateral variations. (2) The lithospheric mantle beneath the Baikal-Mongolia region shows important redox heterogeneities, with a sharp decrease in oxygen fugacity (from +0 to -3 AlogfO2 (FMQ)) during the transition from the spine! to garnet facies peridotites at 50 to 90 km. (3) The speciation of C-O-H fluids changes with depth from essentially H2O-CO2 in the shallow lithospheric mantle to H2O-CH4 at the lithosphere-asthenosphere boundary regardless of the thermal state and the thickness of the lithosphere