No description available.

O nitrogênio compõe cerca de 78% da massa da atmosfera terrestre e é um elemento imprescindível para a construção e manutenção da vida. Porém a abundância de nitrogênio atmosférico da Terra é anômala quando comparada a dos demais planetas telúricos. Isso significa que ou a acresção para esses planetas foi diferente (o que é pouco provável) ou a Terra possui alguma característica única que permita a existência de grandes volumes de nitrogênio em sua atmosfera. A tectônica de placas poderia ser essa característica, uma vez que propicia uma conexão direta entre o manto e superfície (ao mesmo tempo em que material é expelido do manto para a superfície, material é transportado da superfície para o manto). Nesse contexto, este trabalho objetiva compreender, através de simulações em laboratório, o papel das zonas de subducção no transporte global do nitrogênio. Para tal, submeteu-se um material que simula sedimentos pelágicos (esmectitas dioctaédricas) dopado com amônio (NH4-esmectita) a diversas condições de pressão e temperatura: desde pressão ambiente até 7.7 GPa (equivalente a ~270 km de profundidade) e com temperaturas variando entre 200oC e 700oC. Os experimentos foram realizados em uma prensa hidráulica de 1000 tonf com câmaras de perfil toroidal e em um forno de alta temperatura e foram analisados por difração de raios X (DRX), espectroscopia infravermelho por Transformada de Fourier (FTIR) e por imageamento SE-MEV-EDS Além disso, o material inicial foi caracterizado por análise térmica diferencial (DTA) e análise química CHN. Os resultados mostram que as transformações de fase sofridas pela NH4-esmectita agem no sentido de preservar o amônio na estrutura durante o processo de subducção. Também foram observadas fases de pressões mais elevadas capazes de conter amônio (buddingtonita, a 7.7 GPa). Percebeu-se que o regime termal da subducção é fundamental para a eficiência do transporte de nitrogênio, visto que em subducções quentes (litosferas oceânicas jovens que subductam em baixo ângulo) ocorre a fusão parcial do material com liberação de parte do amônio em pressões relativamente baixas (~1 GPa, equivalente a 30 km de profundidade). Por outro lado, em subducções frias (litosferas oceânicas antigas que subductam em alto ângulo) o material aprisiona de forma eficiente o nitrogênio até ~270 km de profundidade (7.7 GPa). / Nitrogen composes around 78 wt% of Earth’s atmosphere and is a vital element for the construction and maintenance of life. However, the abundance of Earth’s atmospheric nitrogen is anomalous when compared to the one from other inner planets. This means that or accretion for these planets was different (which is unlikely) or Earth possesses a unique feature that allows the existence of large volumes of nitrogen in its atmosphere. Plate tectonics could be this feature, since it propitiates a direct connection between mantle and surface (at the same time that material is expelled by the mantle in to the surface, material is transported from the surface in to the mantle). In this context, these work objectives the understanding, through laboratoty simulations, the role of subduction zones in the global transport of nitrogen. For that, a material that simulates pelagic sediments (dioctahedral smectite) doped with ammonium (NH4-smectite) was subjected to a series of pressure and temperature conditions: from ambient pressure up to 7.7 GPa (equivalent to ~270 km depth) and temperatures varying between 200oC and 700oC. Experiments were performed in a 1000 tonf hydraulic press with coupled toroidal chambers and in a high temperature furnace and were analyzed by X ray diffraction (XRD), Fourier Transform infrared spectroscopy (FTIR) and SE-SEM-EDS imaging. Additionally, the starting material was characterized by differential thermal analysis (DTA and CHN chemical analysis Results show that phase transformations suffered by NH4-smectite tend to preserve ammonium inside the mineral structure during subduction. Also, high-pressure ammonium bearing phases were observed (budingtonite at 7.7 GPa). It was perceived that the thermal setting of the subduction is fundamental for the efficiency of nitrogen’s transportation, as in hot subductions (young oceanic lithospheres subducting at low angle) partial melting with partial liberation of ammonium occur in relatively low pressures (~1 GPa, equivalent to 30 km depth). On the other hand, in cold subductions (ancient oceanic lithopsheres subducting at high angles) the material efficiently imprisons nitrogen until ~270 km depth (7.7 GPa).

Primitive, mantle-derived magmas provide important clues about the formation and equilibration conditions of magmas at depth. In subduction zones, it is uncommon for primitive magmas to ascend through the shallow mantle and crust without undergoing chemical modification. Instead, magmas commonly differentiate through fractional crystallization, crustal assimilation, or magma mixing. Those rare primitive lavas that do erupt along a volcanic arc are useful for elucidating subduction-related processes within the mantle wedge (~30–80 km depth) and are the focus of this research. I used piston-cylinder apparatuses to investigate the high-pressure, high-temperature, H2O-undersaturated phase equilibria for several primitive compositions that have erupted at volcanic arcs. I aimed to reveal the permissible residual mantle mineralogy, as well as the P-T- H2O conditions over which the putative mantle melts last equilibrated before erupting. My work focuses on the Trans-Mexican Volcanic Belt (TMVB), where primitive compositions span a range of SiO2, total alkalies (K2O+Na2O), magmatic H2O, and incompatible trace element enrichments. Variations among these components are presumed to result from melting heterogeneous mantle that has been affected, to varying degrees, by a subduction component. Chapter III focuses on the phase equilibria of a Mexican basaltic andesite and an Aleutian basalt. Results show that hydrous basaltic andesite equilibrated with harzburgite in the shallow mantle, whereas the basalt equilibrated with lherzolite. The former appears more common in continental arcs and the latter in intraoceanic arcs. Chapter IV focuses on two alkaline lavas of varying K2O content from the TMVB that are transitional between potassic, hydrous minette and H2O-poor intraplate alkali basalt. Experimental phase relations and trace element modeling reveals that melting and/or mixing of peridotite and clinopyroxene-rich veins are likely involved in producing these transitional lava types. These experimental data are integrated with other petrologic and geophysical data to provide an along-arc perspective of mantle-melt equilibration in the TMVB. Primitive melts appear to commonly equilibrate with chemically heterogeneous mantle at depths above the "hot nose" of the mantle wedge. It is apparent that the shallow mantle wedge is a key component for understanding the geochemical complexities of subduction zone magmas. This dissertation includes previously published and unpublished co-authored material.

No description available.

The objective of this thesis is to calibrate two oxygen barometers for kimberlite magmas in the system CaO-MgO-Al2O3-SiO2-TiO2-FeO based on the Fe and V content of monticellite, CaMgSiO4, that may be utilized in cases where oxides in olivine phenocrysts and perovskite are absent from a kimberlite pipe. I first calibrate a new oxygen barometer for kimberlite magmas based on the Fe content of monticellite in equilibrium with kimberlite liquids in experiments at 100kPa from 1230 to 1350C and at fO2 from NNO-4.1 to NNO+5.3 (where NNO is the nickel-nickel oxide buffer). The XFeMtc/XFeliq (where XFeMtc/XFeliq is the ratio of mole fraction of total Fe in monticellite and Fe in liquid) decreases with increasing fO2, consistent with only Fe2+ entering the monticellite structure. Although the XFe in monticellite varies with temperature and bulk composition, these dependencies are small (0.03) compared to that with fO2. The experimental data were fitted by weigted least square regression to the following relationship: DNNO= (log (0.858(0.021)*XFeliq/XFeMtc-1)-0.139(0.022))/0.193(0.004) (uncertainties at 2 sigma). I apply this oxygen barometer to natural kimberlite assuming the bulk rock FeO is that of their liquid FeO. Monticellite compositions of five kimberlites from both literature and my own investigations revealed a range in fO2 from NNO-3.5 to NNO+1.7. I finally use my well-defined monticellite-liquid Kd Fe2+-Mg to derive a range of Mg/(Mg+Fe2+) (Mg number) for kimberlite melts of 0.40-0.90. This range in composition is broader than previous estimates of 'primary' kimberlites, reflecting the diverse mantle sources and processes that occur during generation and ascent of kimberlites. Second, I calibrate a new oxygen barometer for kimberlite magmas based on the V content of monticellite in equilibrium with kimberlite liquids doped with 0.5 wt% V2O5 at 100kPa at 1280 and 1350C and at fO2 from NNO-4.1 to NNO_0.5. The DV Mtc/liq (DV Mtc/liq = V (ppm) in monticellite/V (ppm) in liquid) decreases with increasing fO2. The partitioning data can be fitted to a model consistent with V5+ as the dominant species in the melt phase above NNO whereas V4+ dominates below those conditions in kimberlitic magmas. The total DV Mtc/liq, which embodies both DV3+ Mtc/liq and DV4+ Mtc/liq, shows a very slight temperature and bulk composition dependence. The experimental data can be fitted by weighted least square regression to the following relationship: DNNO= (log(0.354(1.785)*Vliq/VMtc-1)-1.172(2.302))/0.111(0.071) (uncertainties at 2 sigma and V in ppm). In order to apply this oxygen barometer rigorously, the V concentrations of the kimberlite melt coexisting with monticellite need to be constrained. In contrast to the Fe-in-monticellite oxygen barometer for which the concentration of Fe in monticellite was close to that of the whole rock composition, the concentration of V in the bulk rock composition reflects mostly the large accumulation of olivine xenocrysts which contain low V concentrations. For that reason, the V-in-monticellite oxygen barometer cannot be applied to natural kimberlites until we find a way to overcome this problem. The vanadium concentrations of kimberlite melts are likely higher than the V concentrations of the whole rock compositions leading to underestimated fO2 values. / Graduate

The Howardite-Eucrite-Diogenite (HED) meteorites are a suite of basalts, cumulates and breccias which originate from one differentiated parent body, and are linked to the asteroid Vesta. The HEDs are petrologically diverse with a range of major, minor and trace element compositions. Early crystallisation ages are recorded and so the HEDs provide us with a unique snapshot into the early solar system. The aim of this thesis is to investigate the petrogenesis of the eucrites and diogenites by addressing two questions. What is the Bulk Silicate Vesta (BSV) composition? What differentiation and magmatic processes have occurred? Putative BSV compositions were derived from the geochemistry of the meteorites and geophysical observations of Vesta. Series of one-atmosphere experiments and thermodynamic models investigated the BSV phase relations. Olivine crystallised at ~1625 °C, followed by orthopyroxene at ~1350 °C and feldspar at ~1125 °C. Low-Ca pyroxene-melt partition coefficients for the minor and trace elements were measured. The compatibility of the REEs and HFSEs in low- Ca pyroxene increased by a factor of three, as temperature decreased from 1300-1125 °C and calcium content increased from Wo_0.5-Wo₈. These partition coefficients were combined with the observed phase relations to perform geochemical trace element calculations of differentiation and magmatic processes. My results suggest that BSV had an Mg#(100*(Mg/(Mg+Fe²⁺)) between 75-80, > 43 wt. % SiO₂, 2.5 x CI refractory lithophile elements, 0.5 wt. % MnO and 0.75 wt. % Cr₂O₃. A three stage model for Vesta's evolution is suggested. Firstly, extensive if not global partial melting of BSV. Then, equilibrium crystallisation of the mantle and fractional crystallisation of mantle-derived melts produced diogenitic cumulates and eucrite liquids, accounting for the range in major and trace element abundances. The re-equilibration of trapped melt in cumulates is also thought to have occurred. Finally, crustal anatexis produced the range in trace element fractionations seen.

Previous studies on complex chemical systems, approximating enriched ultramafic compositions, have shown that the stability fields of certain phyllosilicate minerals may be shifted through solid solution. This project focuses on three hydrous phases predicted to play an important role in water transfer and storage during subduction. Talc, and at higher pressures the 10 A phase, are expected form in enriched abyssal peridotite within the cold interior of a lithospheric slab, whilst the sodic amphibole eckermannite is expected to be present in the overlying hydrated basalt. Multi-anvil and piston cylinder press experiments in the FeO-MgO-SiO2-H2O (FMSH), NaO-MgO-Al2O3-SiO2-H2O (NMASH), and MgO-Al2O3-SiO2-H2O (MASH) systems have sought to determine the effect of solid solution on the stability on talc and the 10 A phase, with comparison to the end-member MgO-SiO2-H2O (MSH) system. The reaction talc + H2O = 10 A phase has been bracketed in the MSH system at 4.8 GPa/560 ˚C and 5 GPa/640 ˚C, confirming the estimated reaction position from Pawley et al. (2011). Previously unknown values for the entropy and enthalpy of formation of the 10 A phase have been calculated as DeltaHf = -6172.02 kJ and DeltaSf = 320.075 JK-1. At 2 GPa talc containing 0.48 apfu Fe2+ breaks down in the divariant field talc + anthophyllite + quartz + H2O from ~550 ˚C, initiating talc dehydration at temperatures ~270 ˚C lower than in the MSH system. At 4 GPa Fe-bearing talc breaks down in the divariant field talc + enstatite + coesite. A run at 5.2 GPa and 555 ˚C produced 10 A phase containing 0.48 apfu Fe2+. Between 575 ˚C and 600 ˚C at 6.5 GPa phase reversal experiments bracketed the initiation of Fe-bearing 10 A phase dehydration in the divariant field 10 A phase + enstatite + coesite + H2O, corresponding to a reduction in thermal stability of around ~100 ˚C compared to the end-member. The relative positions of the talc and 10 A phase dehydration reactions suggest the latter is able to accommodate greater Fe substitution, and is therefore more stable in the FMSH system. The assemblages 10 A phase + enstatite + coesite + jadeite and 10 A phase + enstatite + pyrope + coesite, were synthesised in the NMASH and MASH systems, respectively. Compositional analysis indicates that the 10 Å phase in these samples contains < 1 weight % Al2O3, with negligible Na. This suggests that Al3+ substitution in talc and the 10 Å phase is unlikely to exert the same stabilising effect observed in a number of other phyllosilicates. Eckermannite was produced in further NMASH experiments at 6.2 GPa. Compositional and structural analysis indicates near-full A-site occupancy and a composition close to that of the end-member, deviating through a minor binary exchange towards Mg-katophorite. This exchange is proposed to stabilise eckermannite to high pressures, beyond previously published limits for sodic amphibole stability. Updated stability fields for talc, the 10 Å phase, and eckermannite were applied to a thermal model for subduction. This predicts that 10 Å phase containing 0.48 apfu Fe2+ may be stable to depths of ~260 km, compared to ~280 km for the end-member. With increasing pressure and temperature Fe-bearing 10 Å phase will dehydrate across a depth range, resulting in either total de-volatilisation, or transfer to other stable high pressure hydrous phases enabling the transport of water to the deeper regions of the mantle.

O nitrogênio compõe cerca de 78% da massa da atmosfera terrestre e é um elemento imprescindível para a construção e manutenção da vida. Porém a abundância de nitrogênio atmosférico da Terra é anômala quando comparada a dos demais planetas telúricos. Isso significa que ou a acresção para esses planetas foi diferente (o que é pouco provável) ou a Terra possui alguma característica única que permita a existência de grandes volumes de nitrogênio em sua atmosfera. A tectônica de placas poderia ser essa característica, uma vez que propicia uma conexão direta entre o manto e superfície (ao mesmo tempo em que material é expelido do manto para a superfície, material é transportado da superfície para o manto). Nesse contexto, este trabalho objetiva compreender, através de simulações em laboratório, o papel das zonas de subducção no transporte global do nitrogênio. Para tal, submeteu-se um material que simula sedimentos pelágicos (esmectitas dioctaédricas) dopado com amônio (NH4-esmectita) a diversas condições de pressão e temperatura: desde pressão ambiente até 7.7 GPa (equivalente a ~270 km de profundidade) e com temperaturas variando entre 200oC e 700oC. Os experimentos foram realizados em uma prensa hidráulica de 1000 tonf com câmaras de perfil toroidal e em um forno de alta temperatura e foram analisados por difração de raios X (DRX), espectroscopia infravermelho por Transformada de Fourier (FTIR) e por imageamento SE-MEV-EDS Além disso, o material inicial foi caracterizado por análise térmica diferencial (DTA) e análise química CHN. Os resultados mostram que as transformações de fase sofridas pela NH4-esmectita agem no sentido de preservar o amônio na estrutura durante o processo de subducção. Também foram observadas fases de pressões mais elevadas capazes de conter amônio (buddingtonita, a 7.7 GPa). Percebeu-se que o regime termal da subducção é fundamental para a eficiência do transporte de nitrogênio, visto que em subducções quentes (litosferas oceânicas jovens que subductam em baixo ângulo) ocorre a fusão parcial do material com liberação de parte do amônio em pressões relativamente baixas (~1 GPa, equivalente a 30 km de profundidade). Por outro lado, em subducções frias (litosferas oceânicas antigas que subductam em alto ângulo) o material aprisiona de forma eficiente o nitrogênio até ~270 km de profundidade (7.7 GPa). / Nitrogen composes around 78 wt% of Earth’s atmosphere and is a vital element for the construction and maintenance of life. However, the abundance of Earth’s atmospheric nitrogen is anomalous when compared to the one from other inner planets. This means that or accretion for these planets was different (which is unlikely) or Earth possesses a unique feature that allows the existence of large volumes of nitrogen in its atmosphere. Plate tectonics could be this feature, since it propitiates a direct connection between mantle and surface (at the same time that material is expelled by the mantle in to the surface, material is transported from the surface in to the mantle). In this context, these work objectives the understanding, through laboratoty simulations, the role of subduction zones in the global transport of nitrogen. For that, a material that simulates pelagic sediments (dioctahedral smectite) doped with ammonium (NH4-smectite) was subjected to a series of pressure and temperature conditions: from ambient pressure up to 7.7 GPa (equivalent to ~270 km depth) and temperatures varying between 200oC and 700oC. Experiments were performed in a 1000 tonf hydraulic press with coupled toroidal chambers and in a high temperature furnace and were analyzed by X ray diffraction (XRD), Fourier Transform infrared spectroscopy (FTIR) and SE-SEM-EDS imaging. Additionally, the starting material was characterized by differential thermal analysis (DTA and CHN chemical analysis Results show that phase transformations suffered by NH4-smectite tend to preserve ammonium inside the mineral structure during subduction. Also, high-pressure ammonium bearing phases were observed (budingtonite at 7.7 GPa). It was perceived that the thermal setting of the subduction is fundamental for the efficiency of nitrogen’s transportation, as in hot subductions (young oceanic lithospheres subducting at low angle) partial melting with partial liberation of ammonium occur in relatively low pressures (~1 GPa, equivalent to 30 km depth). On the other hand, in cold subductions (ancient oceanic lithopsheres subducting at high angles) the material efficiently imprisons nitrogen until ~270 km depth (7.7 GPa).

O nitrogênio compõe cerca de 78% da massa da atmosfera terrestre e é um elemento imprescindível para a construção e manutenção da vida. Porém a abundância de nitrogênio atmosférico da Terra é anômala quando comparada a dos demais planetas telúricos. Isso significa que ou a acresção para esses planetas foi diferente (o que é pouco provável) ou a Terra possui alguma característica única que permita a existência de grandes volumes de nitrogênio em sua atmosfera. A tectônica de placas poderia ser essa característica, uma vez que propicia uma conexão direta entre o manto e superfície (ao mesmo tempo em que material é expelido do manto para a superfície, material é transportado da superfície para o manto). Nesse contexto, este trabalho objetiva compreender, através de simulações em laboratório, o papel das zonas de subducção no transporte global do nitrogênio. Para tal, submeteu-se um material que simula sedimentos pelágicos (esmectitas dioctaédricas) dopado com amônio (NH4-esmectita) a diversas condições de pressão e temperatura: desde pressão ambiente até 7.7 GPa (equivalente a ~270 km de profundidade) e com temperaturas variando entre 200oC e 700oC. Os experimentos foram realizados em uma prensa hidráulica de 1000 tonf com câmaras de perfil toroidal e em um forno de alta temperatura e foram analisados por difração de raios X (DRX), espectroscopia infravermelho por Transformada de Fourier (FTIR) e por imageamento SE-MEV-EDS Além disso, o material inicial foi caracterizado por análise térmica diferencial (DTA) e análise química CHN. Os resultados mostram que as transformações de fase sofridas pela NH4-esmectita agem no sentido de preservar o amônio na estrutura durante o processo de subducção. Também foram observadas fases de pressões mais elevadas capazes de conter amônio (buddingtonita, a 7.7 GPa). Percebeu-se que o regime termal da subducção é fundamental para a eficiência do transporte de nitrogênio, visto que em subducções quentes (litosferas oceânicas jovens que subductam em baixo ângulo) ocorre a fusão parcial do material com liberação de parte do amônio em pressões relativamente baixas (~1 GPa, equivalente a 30 km de profundidade). Por outro lado, em subducções frias (litosferas oceânicas antigas que subductam em alto ângulo) o material aprisiona de forma eficiente o nitrogênio até ~270 km de profundidade (7.7 GPa). / Nitrogen composes around 78 wt% of Earth’s atmosphere and is a vital element for the construction and maintenance of life. However, the abundance of Earth’s atmospheric nitrogen is anomalous when compared to the one from other inner planets. This means that or accretion for these planets was different (which is unlikely) or Earth possesses a unique feature that allows the existence of large volumes of nitrogen in its atmosphere. Plate tectonics could be this feature, since it propitiates a direct connection between mantle and surface (at the same time that material is expelled by the mantle in to the surface, material is transported from the surface in to the mantle). In this context, these work objectives the understanding, through laboratoty simulations, the role of subduction zones in the global transport of nitrogen. For that, a material that simulates pelagic sediments (dioctahedral smectite) doped with ammonium (NH4-smectite) was subjected to a series of pressure and temperature conditions: from ambient pressure up to 7.7 GPa (equivalent to ~270 km depth) and temperatures varying between 200oC and 700oC. Experiments were performed in a 1000 tonf hydraulic press with coupled toroidal chambers and in a high temperature furnace and were analyzed by X ray diffraction (XRD), Fourier Transform infrared spectroscopy (FTIR) and SE-SEM-EDS imaging. Additionally, the starting material was characterized by differential thermal analysis (DTA and CHN chemical analysis Results show that phase transformations suffered by NH4-smectite tend to preserve ammonium inside the mineral structure during subduction. Also, high-pressure ammonium bearing phases were observed (budingtonite at 7.7 GPa). It was perceived that the thermal setting of the subduction is fundamental for the efficiency of nitrogen’s transportation, as in hot subductions (young oceanic lithospheres subducting at low angle) partial melting with partial liberation of ammonium occur in relatively low pressures (~1 GPa, equivalent to 30 km depth). On the other hand, in cold subductions (ancient oceanic lithopsheres subducting at high angles) the material efficiently imprisons nitrogen until ~270 km depth (7.7 GPa).

abstract: An exhaustive parameter study involving 133 dynamic crystallization experiments was conducted, to investigate the validity of the planetary embryo bow shock model by testing whether the cooling rates predicted by this model are consistent with the most dominant chondrule texture, porphyritic. Results show that using coarse-grained precursors and heating durations ≤ 5 minutes at peak temperature, porphyritic textures can be reproduced at cooling rates ≤ 600 K/hr, rates consistent with planetary embryo bow shocks. Porphyritic textures were found to be commonly associated with skeletal growth, which compares favorably to features in natural chondrules from Queen Alexandra Range 97008 analyzed, which show similar skeletal features. It is concluded that the experimentally reproduced porphyritic textures are consistent with those of natural chondrules. This work shows heating duration is a major determinant of chondrule texture and the work further constrains this parameter by measuring the rate of chemical dissolution of relict grains. The results provide a robust, independent constraint that porphyritic chondrules were heated at their peak temperatures for ≤ 10 minutes. This is also consistent with heating by bow shocks. The planetary embryo bow shock model therefore remains a viable chondrule mechanism for the formation of the vast majority of chondrules, and the results presented here therefore strongly suggest that large planetary embryos were present and on eccentric orbits during the first few million years of the Solar System’s history. / Dissertation/Thesis / Masters Thesis Geological Sciences 2018