This research is concerned with the mechanisms of diffusion in the Earth and the implications of such an understanding. Specifically, this work is concerned with one particular aspect of diffusion: Grain Boundary Diffusion (GBD). An experimental investigation of GBD has been conducted by considering three specific scenarios; GBD of H in stoichiometric Mg-spinel, GBD of Ti in Quartz and GBD of Li in olivine. By considering the GBD of three very different elements it has been possible to synthesise an understanding of some of the mechanisms involved in the process. GBD is potentially a very important process within the Earth with wide ranging implications. Grain boundaries may provide fast pathways for transportation of a range of compatible and incompatible diffusing species in the Earth’s interior – potentially acting as storage locations and also as efficient pathways between different geological reservoirs. It is also potentially very important in the application of a number of techniques including dating and geothermometry and geobarometry. Here, an experimental study of the GBD of H has been carried out with the overall finding that GBD appears to occur at slightly greater yet broadly similar rates to lattice diffusion. This finding is considered in terms of the mantle properties which are affected by the presence and transport of H. A follow up series of experiments was conducted looking at Li diffusion. Li was chosen due to its volatile nature and larger atomic radius as compared to H. As such, it provided a useful test of the hypothesis that the radius of a diffusant might affect its chosen method of diffusion. A third set of experiments were carried out to investigate the GBD of Ti in quartz with particular reference to the TitaniQ geothermo(baro)meter. This set of experiments provided a very useful comparison to the data which had previously been obtained from lighter elements. This investigation has found that a combination of factors including charge, diffusant diameter and the specific mineralogical characteristics of the host phase will define the dominant diffusive mechanism and the size of the contribution made by that mechanism towards observed bulk diffusivities. A characterisation of the temperature dependency of diffusion within each setting has also been completed. As such, it also makes a useful contribution to the current dataset for GBD.

Abstract Geochemical, microstructural and petrological analyses were conducted on metapelites from the Strafford Dome, Vermont. Samples record metamorphic conditions from biotite to peak kyanite/staurolite grade and preserve microstructures related to two Acadian nappe emplacement events. The purpose of this study was to test the validity and application of the Ti-in-quartz (“TitaniQ”) thermobarometer to constraining pressure-temperature-timing-deformation (P-T-t-D) paths in metamorphic tectonites. Due to the nearly ubiquitous presence of quartz in continental rocks, the ability to apply this method would have significant implications for improving our ability to resolve tectonic histories. Cathodoluminescence (CL) imaging on quartz was conducted to qualitatively assess the distribution of Ti in a single grain and/or compare neighboring crystals. X-ray mapping of garnet porphyroblasts was conducted to estimate P-T conditions during garnet growth to provide a framework for included quartz grains. P-T-X contour diagrams (used in P-T calculations for garnet growth) were constructed from data obtained by X-ray fluorescence analysis on bulk-rock chemistries. Secondary ion mass spectrometry analysis was conducted to constrain Ti concentrations in quartz due to the low [Ti] present in the Strafford samples (<10 ppm). Analysis of the samples revealed [Ti] in zoned quartz grains that can be grouped and associated with certain P-T-D conditions. A majority of quartz grains have dark cores in CL images with low [Ti] (~2.5–3.5 ppm) in both matrix quartz and inclusions. Quartz inclusions in garnets that grew syn-tectonically with D2 have bright rims ~5.5 ppm. Matrix quartz, on the other hand, has rims with much higher [Ti] (~7.5–9.5 ppm). Comparing these Ti concentrations to summary P-T paths from previous studies suggests: quartz inclusions have rims recrystallized during the end of D1 deformation, matrix grains have rims re-equilibrated at peak P-T conditions post-D2 deformation, and the dark cores observed in CL images must be from early prograde or relics of the protolith. The evaluation of the TitaniQ thermobarometer’s application to constrain P-T-t-D histories has highlighted some potential problems and significant benefits. To use the thermobarometer, either T or P must be independently constrained, which is often difficult to do given the many microstructural contexts of quartz in a single sample. This study capitalized on the ability to determine the relative timing of quartz (re)crystallization relative to garnet growth. Using another trace element thermobarometer would be ideal (e.g. Zr-in-rutile) for greater precision, although the relevant accessory phases may not be present and constraining the timing of re-equilibration is challenging. The abundance of quartz in continental rocks and the various microstructural occurrences of quartz in a single metamorphic tectonite provides additional opportunities to constrain points on the P-T-D path than conventional thermobarometers. The TitaniQ thermobarometer has the potential to yield deeper insights into the tectonic history of crustal rocks than previously available. These findings further elucidate the potential of the method for use in studies of metamorphic tectonites, continental tectonics and rheology.

No description available.

A Faixa Araçuaí foi formada no Neoproterozóico a partir da colisão E-W entre os continentes Sul-Americano e Africano. Sua porção leste compreende uma extensa área migmatítica (~300 km de comprimento por 50-100 km de largura) onde afloram anatexitos e leucogranitos (unidade Carlos Chagas), kinzigitos e granulitos migmatizados, que provavelmente são o registro de uma ampla fusão parcial da crosta intermediária a inferior. Observações de campo associadas com evidências micro-estruturais indicam que a deformação ocorreu quando as rochas estavam incompletamente solidificadas. Estimativas de temperaturas sincinemáticas realizadas a partir do geotermômetro TitaniQ (titânio-em-quartzo) indicam que a temperatura mínima para a cristalização de cristais de quartzo é ~750°C. Tais temperaturas combinadas com composição química de leucossomas dos anatexitos sugerem que a viscosidade das rochas crustais foi reduzida para pelo menos 108 Pa s. Baixo valor de viscosidade associado às evidências de campo e de micro-estruturas são consistentes com a geração de no mínimo 30% de volume de magma durante a orogênese. Grandes quantidades de magma promovem um drástico enfraquecimento da resistência mecânica das rochas à deformação, e atestam que a crosta anatética do extremo leste da Faixa Araçuaí representa um análogo de litosferas quentes (hot orogen), tal como a Himalaiana. Investigação mineralógica detalhada permitiu caracterizar um comportamento dominantemente paramagnético para os anatexitos e ferromagnético para os granulitos. Medidas de orientação preferencial cristalográfica (OPC) a partir da técnica de EBSD (electron backscatter diffraction) revelam que a foliação magnética surge, sobretudo, a partir da orientação preferencial dos eixos [001] da biotita orientados perpendicularmente ao plano de fluxo. Contudo, dada a fraca anisotropia linear desse mineral, apenas uma secundária contribuição de sua subtrama foi observada para a origem da lineação magnética (k1). A correspondência entre os eixos [001] de feldspatos e k1 ocorre devido a OPC de pequenas inclusões de ilmenita que imitam a OPC de seus minerais hospedeiros. Correlação entre k1 da Anisotropia de Remanência Anistéretica (ARA) e k1 da Anisotropia de Suscetibilidade Magnética (ASM) demonstra que, na escala do espécime, a lineação magnética tem uma contribuição da anisotropia dos minerais ferromagnéticos. Assim sendo, a lineação magnética nos anatexitos é o resultado da combinação da trama cristalográfica de feldspatos e de biotita com o alinhamento preferencial de grãos ferromagnéticos. Medidas de ASM realizadas para recuperar a trama mineral e investigar o fluxo nos migmatitos revela um padrão de deformação complexo, no qual, em função das direções de lineação, especialmente, é possível caracterizar três setores estruturais. A porção norte (região estrutural 1) com foliações dominantemente sub-horizontais e lineação fortemente orientada na direção NW-SE representa uma região de escape tectônico que ocorre através de um fluxo horizontal de canal (channel flow). Fluxos de canais possivelmente resultam da atuação de forças gravitacionais (gravity-driven flow). O setor sul (regiões estruturais 2 e 3) com variadas direções de foliação (NE-SW, E-W e NW-SE) e lineações com caimentos para Norte e Oeste, provavelmente refletem um regime de fluxo influenciado, sobretudo, pela tectônica de convergência E-W (collision-driven flow). Ambos os setores sugerem que na escala regional o fluxo crustal registrado pelos migmatitos resulta de um regime de deformação que envolve forças gravitacionais, devido a carga topográfica da crosta superior sobreposta à crosta intermediária parcialmente fundida, com viscosidade baixa, e forças tectônicas, associadas à colisão entre os continentes Sul-Americano e Africano. / The Araçuaí belt was formed by the collision between South American and African protocontinents during the Neoproterozoic. Its eastern part consists of an extensive migmatitic area (~300 km long x 50-100 km wide) where crop out anatexites and leucogranites (Carlos Chagas unit), migmatitic kinzigites and granulites that probably are the record of a widespread partial melting of the middle to lower crust. Field observations associated with microstructural evidences indicate that the deformation occurred when the rocks were incompletely solidified. Synkinematic temperature estimates realized using the TitaniQ (titaniun-in-quartz) geotermomether suggest that the minimum temperature for the quartz crystallization is ~750°C. Such temperatures combined with bulk rock composition of leucosome in the anatexites suggest that the viscosity of crustal rocks was dropped to at least 108 Pa s. Low viscosity values associated with field and microstructural evidences are consistent with the generation of at least 30% volume of melt during the orogeny. The presence of large volumes of melt promotes a drastic weakening of the mechanical strength of rocks and suggests that the anatectic crust of the eastern Araçuaí belt represents an analogue of present day hot orogen such the Himalayas. Detailed mineralogy investigation permitted to characterize the paramagnetic behaviour of the anatexites and the ferromagnetic behaviour of the granulites. Crystallographic preferred orientation (CPO) measurements using the EBSD (Electron Backscatter Diffraction) technique reveal that the magnetic foliation results from the preferred orientation of the biotite [001] oriented normal to the flow plane. However, given the feeble linear anisotropy of this mineral, only a subsidiary contribution of its subfabric to the origin of the magnetic lineation (k1) was observed. Correspondence between [001] of feldspars and k1 is due to the CPO of small inclusions of ilmenite that mimic the CPO of their host minerals. Correlation between k1 of the Anisotropy of Anhysteretic Remanent Magnetization (AARM) and k1 of the Anisotropy of Magnetic Susceptibility (AMS) demonstrate that, at the specimen scale, the magnetic lineation has a contribution of the anisotropy of the ferromagnetic minerals. AMS measurements realized to recover the mineral fabric and investigate the migmatitic flow field revealed a complex strain pattern in which, considering the lineation trends, especially, it is possible to characterize three structural sectors. The north region (structural sector 1) with foliations dominantly sub-horizontal and lineation trending NW-SE is interpreted as a region of tectonic escape that may represent a horizontal channel flow. This oblique tectonic escape probably results from gravity forces (gravity-driven flow). The Southern region (structural sectors 2 and 3) with variable trending foliations (NE-SW, E-W and NW-SE) and lineation plunging to North and West, probably reflect a flow regime dominantly influenced by the E-W convergence of the African and South-American continents (collision-driven flow). Altogether, the characteristics of the various domains suggest that the deformation of the partially molten middle crust of the Araçuaí belt was the result of the combination of gravity forces due to the topographic load and tectonic forces due to the convergence between the African and South-American continents.

A Faixa Araçuaí foi formada no Neoproterozóico a partir da colisão E-W entre os continentes Sul-Americano e Africano. Sua porção leste compreende uma extensa área migmatítica (~300 km de comprimento por 50-100 km de largura) onde afloram anatexitos e leucogranitos (unidade Carlos Chagas), kinzigitos e granulitos migmatizados, que provavelmente são o registro de uma ampla fusão parcial da crosta intermediária a inferior. Observações de campo associadas com evidências micro-estruturais indicam que a deformação ocorreu quando as rochas estavam incompletamente solidificadas. Estimativas de temperaturas sincinemáticas realizadas a partir do geotermômetro TitaniQ (titânio-em-quartzo) indicam que a temperatura mínima para a cristalização de cristais de quartzo é ~750°C. Tais temperaturas combinadas com composição química de leucossomas dos anatexitos sugerem que a viscosidade das rochas crustais foi reduzida para pelo menos 108 Pa s. Baixo valor de viscosidade associado às evidências de campo e de micro-estruturas são consistentes com a geração de no mínimo 30% de volume de magma durante a orogênese. Grandes quantidades de magma promovem um drástico enfraquecimento da resistência mecânica das rochas à deformação, e atestam que a crosta anatética do extremo leste da Faixa Araçuaí representa um análogo de litosferas quentes (hot orogen), tal como a Himalaiana. Investigação mineralógica detalhada permitiu caracterizar um comportamento dominantemente paramagnético para os anatexitos e ferromagnético para os granulitos. Medidas de orientação preferencial cristalográfica (OPC) a partir da técnica de EBSD (electron backscatter diffraction) revelam que a foliação magnética surge, sobretudo, a partir da orientação preferencial dos eixos [001] da biotita orientados perpendicularmente ao plano de fluxo. Contudo, dada a fraca anisotropia linear desse mineral, apenas uma secundária contribuição de sua subtrama foi observada para a origem da lineação magnética (k1). A correspondência entre os eixos [001] de feldspatos e k1 ocorre devido a OPC de pequenas inclusões de ilmenita que imitam a OPC de seus minerais hospedeiros. Correlação entre k1 da Anisotropia de Remanência Anistéretica (ARA) e k1 da Anisotropia de Suscetibilidade Magnética (ASM) demonstra que, na escala do espécime, a lineação magnética tem uma contribuição da anisotropia dos minerais ferromagnéticos. Assim sendo, a lineação magnética nos anatexitos é o resultado da combinação da trama cristalográfica de feldspatos e de biotita com o alinhamento preferencial de grãos ferromagnéticos. Medidas de ASM realizadas para recuperar a trama mineral e investigar o fluxo nos migmatitos revela um padrão de deformação complexo, no qual, em função das direções de lineação, especialmente, é possível caracterizar três setores estruturais. A porção norte (região estrutural 1) com foliações dominantemente sub-horizontais e lineação fortemente orientada na direção NW-SE representa uma região de escape tectônico que ocorre através de um fluxo horizontal de canal (channel flow). Fluxos de canais possivelmente resultam da atuação de forças gravitacionais (gravity-driven flow). O setor sul (regiões estruturais 2 e 3) com variadas direções de foliação (NE-SW, E-W e NW-SE) e lineações com caimentos para Norte e Oeste, provavelmente refletem um regime de fluxo influenciado, sobretudo, pela tectônica de convergência E-W (collision-driven flow). Ambos os setores sugerem que na escala regional o fluxo crustal registrado pelos migmatitos resulta de um regime de deformação que envolve forças gravitacionais, devido a carga topográfica da crosta superior sobreposta à crosta intermediária parcialmente fundida, com viscosidade baixa, e forças tectônicas, associadas à colisão entre os continentes Sul-Americano e Africano. / The Araçuaí belt was formed by the collision between South American and African protocontinents during the Neoproterozoic. Its eastern part consists of an extensive migmatitic area (~300 km long x 50-100 km wide) where crop out anatexites and leucogranites (Carlos Chagas unit), migmatitic kinzigites and granulites that probably are the record of a widespread partial melting of the middle to lower crust. Field observations associated with microstructural evidences indicate that the deformation occurred when the rocks were incompletely solidified. Synkinematic temperature estimates realized using the TitaniQ (titaniun-in-quartz) geotermomether suggest that the minimum temperature for the quartz crystallization is ~750°C. Such temperatures combined with bulk rock composition of leucosome in the anatexites suggest that the viscosity of crustal rocks was dropped to at least 108 Pa s. Low viscosity values associated with field and microstructural evidences are consistent with the generation of at least 30% volume of melt during the orogeny. The presence of large volumes of melt promotes a drastic weakening of the mechanical strength of rocks and suggests that the anatectic crust of the eastern Araçuaí belt represents an analogue of present day hot orogen such the Himalayas. Detailed mineralogy investigation permitted to characterize the paramagnetic behaviour of the anatexites and the ferromagnetic behaviour of the granulites. Crystallographic preferred orientation (CPO) measurements using the EBSD (Electron Backscatter Diffraction) technique reveal that the magnetic foliation results from the preferred orientation of the biotite [001] oriented normal to the flow plane. However, given the feeble linear anisotropy of this mineral, only a subsidiary contribution of its subfabric to the origin of the magnetic lineation (k1) was observed. Correspondence between [001] of feldspars and k1 is due to the CPO of small inclusions of ilmenite that mimic the CPO of their host minerals. Correlation between k1 of the Anisotropy of Anhysteretic Remanent Magnetization (AARM) and k1 of the Anisotropy of Magnetic Susceptibility (AMS) demonstrate that, at the specimen scale, the magnetic lineation has a contribution of the anisotropy of the ferromagnetic minerals. AMS measurements realized to recover the mineral fabric and investigate the migmatitic flow field revealed a complex strain pattern in which, considering the lineation trends, especially, it is possible to characterize three structural sectors. The north region (structural sector 1) with foliations dominantly sub-horizontal and lineation trending NW-SE is interpreted as a region of tectonic escape that may represent a horizontal channel flow. This oblique tectonic escape probably results from gravity forces (gravity-driven flow). The Southern region (structural sectors 2 and 3) with variable trending foliations (NE-SW, E-W and NW-SE) and lineation plunging to North and West, probably reflect a flow regime dominantly influenced by the E-W convergence of the African and South-American continents (collision-driven flow). Altogether, the characteristics of the various domains suggest that the deformation of the partially molten middle crust of the Araçuaí belt was the result of the combination of gravity forces due to the topographic load and tectonic forces due to the convergence between the African and South-American continents.