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The work reported in this thesis applies a new isotope tracer, stable strontium isotopes (δ^88/86Sr), to address questions concerning changes in global climate that occur in response to continental weathering processes, and to constrain the modern marine geochemical Sr cycle. Stable Sr isotopes are a relatively new geochemical proxy, and as such their behavior needs to be understood in differing forms of marine calcium carbonate, the archives from which records of past stable Sr variability in the oceans can be constructed. Foraminifera, coccoliths and corals (both aragonite and high Mg calcite) acquire δ^88/86Sr values lighter than that of modern day seawater, (approximately 0.11, 0.05, 0.2 and 0.19 ‰ lighter than seawater at ~25°C respectively) providing a measureable offset which can be used to constrain the modern Sr outputs from the ocean and provide a better understanding of the modern Sr cycle. Using foraminifera as a sedimentary archive the first marine δ^88/86Sr record of seawater over the last two glacial cycles has been constructed, and used to investigate changing carbonate input and output over this 145 kyr period. Modelling of the large excursion of δ^88/86Sr to heavier values during Marine Isotope Stage (MIS) 3, reveals that this is more likely to be due to local changes in seawater or post-depositional alteration, rather then whole ocean changes. In the terrestrial environment δδ88/86^Sr has been measured in the dissolved load of rivers from the Himalaya. It is found that, in general, rivers draining carbonate catchments possess lighter isotopic δ^88/86Sr values than those from rivers draining silicates. Covariations of either δ88/86Sr vs. δ30Si or δ^88/86Sr vs. 1/[Sr] can be used to distinguish between rivers draining different catchment areas.

Due to the recent success, in terms of accuracy and precision, of a number of strontium optical lattice optical frequency standards, and the classification of the 5s² ¹S₀ to 5s5p ³P₀ transition in neutral strontium as a secondary definition of the SI unit of the second, many new strontium lattice clocks are under development. The strontium optical lattice clock (Sr OLC) at the National Physical Laboratory (NPL) is one such project. This thesis describes the design and build of the NPL Sr OLC, discussing the considerations behind the design. Details of the first cooling stage are given, which includes the characterisation of a novel permanent-magnet Zeeman slower by measurements of the longitudinal velocity distributions and loading of the MOT at 461 nm. Development of a narrow linewidth laser system at 689 nm is described, which is used for initial spectroscopy of the second-stage cooling transition. In particular, this work describes progress towards two independent ultra-narrow linewidth clock lasers. The new generation of strontium lattice clock experiments have focused on characterising the systematic frequency shifts and reducing their associated fractional frequency uncertainties, as well as reducing the fractional frequency instability of the measurement. One focus of the Sr OLC at NPL is to help characterise the frequency shift of the clock transition due to black-body radiation (BBR), which is currently the largest contributor to the uncertainty budget of the measured clock frequency. Our approach, discussed here, is to make a direct, differential measurement of the shift with the atoms housed alternately in environments of differing temperatures. Better characterisation and control of the BBR frequency shift of the strontium clock transition is crucial for the future of the Sr OLC as a leading frequency standard.

Strontium isotope analysis has provided archaeologists with an unprecedented opportunity to study the mobility of humans and animals in the past. However, a lack of systematic environmental baseline data has seriously restricted the full potential of the analytical technique; there is little biosphere data available against which to compare measured skeletal data. This thesis examines the extent to which geographic variation in biosphere 87Sr/86Sr composition can be spatially resolved within the lowland terrain of England, in a geographically and geologically coherent study area. Systematically collected samples of vegetation, stream water and surface soils, including new and archived material have been used. The potential of these sample media to provide reliable estimates of the ⁸⁷Sr/⁸⁶Sr composition of bioavailable strontium are evaluated under both high-density and low-density sampling regimes, and against new analyses of local archaeological material. Areas lying south of the Anglian glacial limit, display a pattern of geographic ⁸⁷Sr/⁸⁶Sr biosphere variation (0.7080-0.7105) controlled by solid geology, as demonstrated by high-density biosphere mapping. Data collected at a wider geographic scale, including above superficial deposits, indicate the dominant influence of re-worked local rocks on the biosphere. These methods have enabled a reclassification of the archaeologically important Cretaceous Chalk domain. Analysis of rainwater and other indicators of atmospheric deposition show that, in this setting, local biosphere variation is not significantly perturbed by atmospheric inputs. Time-related data from archaeological cattle and sheep/goat tooth enamel suggest that the modern biosphere data can be used to understand livestock management regimes and that these are more powerful than using an average value from the enamel. A more complete understanding of possible patterns of mobility in a group of humans has been achieved through analysis of material from Winchester and comparison with the Chalk biosphere domain.

Student Number : 0201438A - PhD thesis - School of Geosciences - Faculty of Science / This project focuses on the Upper Critical and Lower Main Zones in the eastern Bushveld Complex, South Africa. Lithological and stratigraphic information show that there are distinct differences at this level between the eastern and western limbs of the complex. Geochemical studies are centred on the Merensky and Bastard Cyclic Units in which the platiniferous Merensky Reef occurs. A major geochemical hiatus occurs in the Bushveld Complex at the level of the platiniferous Merensky Reef, close to the Critical/Main Zone boundary. The origin of this hiatus and its relation to mineralisation has not been fully resolved. Geochemical parameters are investigated that allow minerals in the Merensky and Bastard Cyclic Units to be classified as originating from either Critical or Main Zone magmas. Modelling of element ratios (Ni/Y, Cr/Ni, Cr/Co, Y/Co, Cr/V, Co/V and Cr/MgO) demonstrates the varying reliability of using ratios as geochemcial tools to constrain magma influxes within a chamber. However, it is shown that the Cr/MgO ratio is effective in determining real differences across the Critical/Main Zone boundary that are independent of lithology. In addition, initial Sr isotope ratios for plagioclase are significantly different in Critical and Main Zone rocks. Geochemical data through the Merensky and Bastard Cyclic Units indicate that orthopyroxene that originated from magma with composition like that of the Critical Zone magma sometimes occurs together with plagioclase that originated from Main Zone magma. In detail, in the pyroxenite at the base of the Merensky Unit, both plagioclase and orthopyroxene display Critical Zone signatures, but in the overlying part of the Merensky Cyclic Unit, plagioclase increasingly shows a Main Zone signature, whereas orthopyroxene continues to display a Critical Zone signature. Similarly, in the Bastard pyroxenite, Sr isotopes and absolute Sr in plagioclase display a range of values from Main Zone to Critical Zone, but orthopyroxene consistently displays Critical Zone affinity. These observations of mineral disequilibrium clearly show that the two major minerals in the Merensky and Bastard Cyclic Units were formed from two different, but coexisting, magmas. A model that accounts for this disequilibrium is proposed here. It invokes the influx of Main Zone magma at the level of the base of the Merensky unit that dispalced the Critical Zone magma upward, but the two magmas did not mix. The latter continued to crystallise orthopyroxene which sank through the Main Zone influx, due to its density contrast. These crystals collected on the crystal pile to form the Merensky pyroxenite. The Main Zone magma, into which the cumulus Critical Zone orthopyroxene accumulated, crystallised interstitial plagioclase that had a Main Zone Sr isotopic ratio. Whole-rock, major element geochemical data show that a variable proportion of the plagioclase in both the Merensky and Bastard pyroxenites is cumulus. It is inferred to have accumulated with orthopyroxene and has a Critical Zone initial Sr isotope ratio. Thus the two pyroxenites now yield a mixed Sr isotopic signature of Critical Zone cumulus and Main Zone intercumulus and possibly cumulus plagioclase that varies along strike. Above the two pyroxenites, the Sr signature of the norites and anorthosites of both cyclic units is dominated by cumulus plagioclase from the Main Zone magma. It is concluded that the variations in initial Sr isotope ratios do not result from mixing of magmas, but result from accumulation of orthopyroxene and plagioclase from a higher, isotopically distinct layer of magma into an underlying layer. The Merensky and Bastard Cyclic Units therefore display features of Critical or Main Zone magma characteristics depending upon which chemical parameter is considered. These cycles are therefore classified as a Transitional Unit.

O objetivo desta tese de doutorado foi estudar a influência da adição do íon estanho (Sn4+) à rede do composto SrTiO3 em substituição ao íon de titânio visando otimizar as propriedades elétricas desse composto e, como consequência, obter uma melhora de seu desempenho como um sensor de gás na forma de filmes finos. Para realizar a deposição destes filmes finos através dos métodos de Deposição por Feixe de Elétrons (EBD), alvos cerâmicos de composição SrTi1-xSnxO3 (STSO) com x = 0; 0,20; 0,40; 0,60; 0,80; 0,85; 0,90; 0,95; 1 foram obtidos através do método dos precursores poliméricos modificado. A sequência de formação de soluções sólidas foi determinada através do refinamento Rietveld das amostras STSO na forma de pó sinterizadas, obtidas através dos métodos dos precursores poliméricos e de reação de estado sólido, mostrando que a transição da fase cúbica Pm3̄m do composto SrTiO3 até a fase ortorrômbica Pnma do composto SrSnO3 não depende do método de síntese. As medidas de espectroscopia Raman e absorção de raios-X (XANES, na borda K do Ti) das amostras tanto na forma de pó, obtidas através do método dos precursores poliméricos e de reação de estado sólido, quanto na forma de filme fino obtidas por EBD revelaram a existência de uma desordem local na rede do composto SrTiO3 que diminui com o aumento da temperatura e com a diminuição da concentração de Sn. Os filmes finos STSO obtidos por EBD foram avaliados como sensores utilizando-se os gases O3 e NH3. Em medidas realizadas com o gás ozônio (O3), os resultados mostraram que os filmes finos de 100 nm de espessura apresentaram uma maior sensibilidade tendo a amostra com 60% de Sn com o melhor desempenho a 350°C para 0,15 ppm do gás. As análises de performance dos filmes STSO quanto a seletividade indicaram que não foram seletivos e que apresentaram uma maior resposta ao gás ozônio quando comparados ao gás NH3. / The objective of this work was to study the influence of the addition of tin ion (Sn4+) into the SrTiO3 compound lattice, to replace the titanium ion (Ti4+). The aim was to optimize the electrical properties of SrTiO3 compound and, as a consequence, to obtain an improvement of its performance as a gas sensor in the thin films samples. To perform the deposition of these thin films through Electron Beam Deposition (EBD), ceramic targets of composition SrTi1-xSnxO3 (STSO) with x = 0; 0.20; 0.40; 0.60; 0.80; 0.85; 0.90; 0.95; and 1 were obtained by the modified polymer precursor method. The solid solution formation sequence was determined by the Rietveld refinement of the STSO sintered powdered samples, obtained by both polymeric precursor and solid-state reaction methods, showing that the transition from the cubic Pm3̄m phase of the SrTiO3 compound to the orthorhombic Pnma phase of the SrSnO3 compound does not depend on the synthesis method. The measurements of Raman spectroscopy and absorption of X-rays (XANES, at Ti K-edge), of the powdered samples obtained by both synthesis methods and of the thin films obtained by EBD, revealed the existence of a local disorder in the SrTiO3 compound lattice which decreases with increasing of temperature and with decreasing of Sn concentration. The STSO thin films were evaluated as sensors using the O3 and NH3 gases. In measurements accomplished with the ozone gas (O3), the results showed that thin films of 100 nm thickness had a higher sensitivity. The sample having 60% of tin showed the best performance at 350°C for 0.15 ppm of ozone gas. The performance analysis related to the selectivity of the STSO films indicated they were not selective and that presented a higher response to the ozone gas when compared to the NH3 gas.

O processamento em alta pressão é um método alternativo para a produção de materiais cerâmicos. Neste trabalho, pressões na ordem de 7,7 GPa e 2,5 GPa foram aplicadas em amostras, em diferentes temperaturas, que foram colocadas em uma célula de reação específica, gerando diferentes efeitos na formação de fases. A composição de fases foi analisada por difração de raios X e a evolução microestrutural, associada ao processamento em alta pressão, foi investigada por microscopia eletrônica por varredura em associação com a espectroscopia por dispersão de energia. Um analisador de resposta de frequência foi utilizado para obter as curvas ferroelétricas por espectroscopia de impedância eletroquímica. A utilização de alta pressão (2,5 GPa) possibilitou a obtenção de amostras de SrBi2Ta2O9 monofásicas com elevada densidade relativa, acima de 93%, após sinterização a uma temperatura de 900 °C. Essa temperatura é inferior às usualmente necessárias para obter alta densificação utilizando métodos convencionais de sinterização. Além disso, as amostras processadas em alta pressão apresentaram uma resposta dielétrica similar às amostras de SrBi2Ta2O9 sinterizadas por processos convencionais em temperaturas acima de 1000 ºC. / High-pressure processing is a very attractive approach for the production of ceramic materials. In this work, pressures about 7.7 GPa and 2.5 GPa were applied in SrBi2Ta2O9 samples at different temperatures placed in a specific reaction cell. X-ray diffraction was used to identify the different phases produced as a function of the processing conditions. The microstructural evolution, associated to the high-pressure processing, was investigated by scanning electron microscopy in association with energy dispersive spectroscopy. Frequency response analysis was used to obtain the ferroelectric curves by electrochemical impedance spectroscopy. A highly densified (> 93% of theoretical density) single-phase (SrBi2Ta2O9) sample was obtained after processing at 2.5 GPa and 900 ºC. This temperature is lower than those necessary to obtain high densification, when conventional sintering processes are employed. In addition, the samples produced by high pressure processing showed a dielectric response similar to SrBi2Ta2O9 samples sintered by conventional processes at temperatures above 1000 ºC.

O objetivo desta tese de doutorado foi estudar a influência da adição do íon estanho (Sn4+) à rede do composto SrTiO3 em substituição ao íon de titânio visando otimizar as propriedades elétricas desse composto e, como consequência, obter uma melhora de seu desempenho como um sensor de gás na forma de filmes finos. Para realizar a deposição destes filmes finos através dos métodos de Deposição por Feixe de Elétrons (EBD), alvos cerâmicos de composição SrTi1-xSnxO3 (STSO) com x = 0; 0,20; 0,40; 0,60; 0,80; 0,85; 0,90; 0,95; 1 foram obtidos através do método dos precursores poliméricos modificado. A sequência de formação de soluções sólidas foi determinada através do refinamento Rietveld das amostras STSO na forma de pó sinterizadas, obtidas através dos métodos dos precursores poliméricos e de reação de estado sólido, mostrando que a transição da fase cúbica Pm3̄m do composto SrTiO3 até a fase ortorrômbica Pnma do composto SrSnO3 não depende do método de síntese. As medidas de espectroscopia Raman e absorção de raios-X (XANES, na borda K do Ti) das amostras tanto na forma de pó, obtidas através do método dos precursores poliméricos e de reação de estado sólido, quanto na forma de filme fino obtidas por EBD revelaram a existência de uma desordem local na rede do composto SrTiO3 que diminui com o aumento da temperatura e com a diminuição da concentração de Sn. Os filmes finos STSO obtidos por EBD foram avaliados como sensores utilizando-se os gases O3 e NH3. Em medidas realizadas com o gás ozônio (O3), os resultados mostraram que os filmes finos de 100 nm de espessura apresentaram uma maior sensibilidade tendo a amostra com 60% de Sn com o melhor desempenho a 350°C para 0,15 ppm do gás. As análises de performance dos filmes STSO quanto a seletividade indicaram que não foram seletivos e que apresentaram uma maior resposta ao gás ozônio quando comparados ao gás NH3. / The objective of this work was to study the influence of the addition of tin ion (Sn4+) into the SrTiO3 compound lattice, to replace the titanium ion (Ti4+). The aim was to optimize the electrical properties of SrTiO3 compound and, as a consequence, to obtain an improvement of its performance as a gas sensor in the thin films samples. To perform the deposition of these thin films through Electron Beam Deposition (EBD), ceramic targets of composition SrTi1-xSnxO3 (STSO) with x = 0; 0.20; 0.40; 0.60; 0.80; 0.85; 0.90; 0.95; and 1 were obtained by the modified polymer precursor method. The solid solution formation sequence was determined by the Rietveld refinement of the STSO sintered powdered samples, obtained by both polymeric precursor and solid-state reaction methods, showing that the transition from the cubic Pm3̄m phase of the SrTiO3 compound to the orthorhombic Pnma phase of the SrSnO3 compound does not depend on the synthesis method. The measurements of Raman spectroscopy and absorption of X-rays (XANES, at Ti K-edge), of the powdered samples obtained by both synthesis methods and of the thin films obtained by EBD, revealed the existence of a local disorder in the SrTiO3 compound lattice which decreases with increasing of temperature and with decreasing of Sn concentration. The STSO thin films were evaluated as sensors using the O3 and NH3 gases. In measurements accomplished with the ozone gas (O3), the results showed that thin films of 100 nm thickness had a higher sensitivity. The sample having 60% of tin showed the best performance at 350°C for 0.15 ppm of ozone gas. The performance analysis related to the selectivity of the STSO films indicated they were not selective and that presented a higher response to the ozone gas when compared to the NH3 gas.

Óxidos à base de titânio são estudados por suas diversas aplicações. Dentre eles, compostos com estrutura cristalina de perovskita apresentam propriedades elétricas diferenciadas. Ademais, os recém-descobertos nanotubos derivados de TiO2 por método hidrotérmico têm chamado a atenção dos pesquisadores por sua alta área superficial e fácil obtenção, embora ainda haja controvérsias sobre sua estrutura cristalina e a influência das condições de síntese. Com o desenvolvimento tecnológico, tornou-se fundamental a obtenção de materiais mais puros e com propriedades controladas, o que vem sendo alcançado através de rotas brandas, relacionadas à Química Doce. Simultaneamente, a preocupação ambiental vem influenciando as metodologias sintéticas através das diretrizes da Química Verde. Esta pesquisa visa: 1. caracterização de SrTiO3 obtido por rotas brandas - sal fundido, hidrotérmica, precipitação do sol e combustão. Os produtos foram caracterizados por análise de sorção de N2, DRX e termogravimetria, para a comparação de área superficial (BET), perfil de porosidade (DFT), composição cristalina e cristalinidade, tamanho de partículas e composição química. 2. exploração do sistema de nanotubos derivados de TiO2 pelo método hidrotérmico em NaOH 10 mol.L-1. Foram comparados quatro precursores (TiO2 amorfo, anatase e rutilo obtidos via precipitação de alcóxido, e o comercial P25), dois tempos de reação (24h e 72h), e o efeito de lavagem posterior com HCl. As amostras foram caracterizadas por DRX, área superficial (BET), perfil de porosidade (BJH), MEV e MET, além de espectroscopia Raman e TG e o efeito da temperatura na composição cristalina das amostras. A rota de precipitação do sol produziu SrTiO3 com maior grau de cristalinidade e de impurezas, sendo que sua área superficial diminuiu após tratamento a 400°C. Todos os produtos continham SrCO3, eliminado após 900°C. O método da combustão não formou o titanato. Nanotubos de comprimentos variados foram obtidos de todos os precursores cristalinos, sendo que rutilo não gerou outros tipos de nanoestruturas e os nanotubos mais longos. Além disso, foi o polimorfo que reagiu mais lentamente. O precursor amorfo gerou nanoestruturas semelhantes a nanofios. Foi observado que os nanotubos são compostos de titanatos de sódio lamelares, sendo esses cátions trocados por H+ pela lavagem dos pós com HCl. Essa troca iônica promove a diminuição da região interlamelar e o aumento da área superficial das amostras. / Titanium based oxides are studied for their wide range of applications. Among them, perovskite-like oxides show especial electrical properties. Furthermore, the recently discovered TiO2-derived nanotubes through hydrothermal process have been drawing researchers\' attention for their high surface area and because they can be easily obtained, although their crystal structure and the influence of condition synthesis still being point of controversy. Due to technological advances, the production of property-controlled, composition and phase pure materials has become crucial. These aims have been achieved by the employment of soft routes, related to Soft Chemistry synthesis. Simultaneously, environmental concerns have influenced synthetic methodologies through the Green Chemistry guidelines. This research aims: 1. characterizing of SrTiO3 synthesized by soft routes, namely molten salt synthesis, hydrothermal method, sol-precipitation process and combustion synthesis. The products were characterized by N2 sorption analysis, XRD and thermogravimetry in order to compare their surface area (BET), porous structure (DTF), chemical and crystal phase composition, crystallinity and particle size. 2. exploring the system of nanotubes hydrothermally derived from TiO2 in NaOH 10 mol.L-1. The effects of precursor type (amorphous TiO2, anatase and rutile obtained by alcoxide hydrolysis, and commercial P25), reaction time (24h and 72h), and acid washing treatment were compared. The samples were characterized by XRD, surface area (BET), porous structure (BJH), SEM and TEM, besides Raman spectroscopy, TG and temperature effect on the crystal composition. The sol-precipitation route produced the SrTiO3 sample with higher crystallinity and amount of impurities, while its surface area decreased on 400°C heat-treatment. All products showed SrCO3 presence up to 900°C. Combustion synthesis did not lead to the strontium titanate. Varied-length nanotubes and other nanostructures were obtained from all crystalline precursors, although rutile-derived samples showed only nanotubes, and the longest ones. On the other hand, this precursor reacted more slowly than the others. Amorphous TiO2 produced wire-like nanostructures. It has been observed that nanotubes are composed of lamellar sodium titanate, and that HCl washing promotes Na+ exchange for H+ ions. This ion-exchange leads to a decrease in the interlamellar spacing and an increase in the surface area of the samples.