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Abstract: The influence of soil organisms on metal mobility and bioavailability in soils is not currently fully understood. We conducted experiments to determine whether calcium carbonate granules secreted by the earthworm Lumbricus terrestris could incorporate and immobilise lead in lead- and calcium- amended artificial soils. Soil lead concentrations were up to 2000 mg kg-1 and lead:calcium ratios by mass were 0.5-8. Average granule production rates of 0.39 + 0.04 mgcalcite earthworm-1 day-1 did not vary with soil lead concentration. The lead:calcium ratio in granules increased significantly with that of the soil (r2 = 0.81, p = 0.015) with lead concentrations in granules reaching 1577 mg kg-1. X-ray diffraction detected calcite and aragonite in the granules with indications that lead was incorporated into the calcite at the surface of the granules. In addition to the presence of calcite and aragonite X-ray absorption spectroscopy indicated that lead was present in the granules mainly as complexes sorbed to the surface but with traces of lead-bearing calcite and cerussite. The impact that lead-incorporation into earthworm calcite granules has on lead mobility at lead-contaminated sites will depend on the fraction of total soil lead that would be otherwise mobile.

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Abstract: This thesis concerns the electron and X-ray microanalysis of planetary materials: from Comet 81P/Wild2 to the surface of Mars. Advanced techniques in electron microscopy and X-ray spectroscopy have been developed for the microanalysis of the nakhlite martian meteorites and Comet 81P/Wild2 samples from the Stardust Mission. Electron microprobe analysis and a Focussed Ion Beam - Scanning Electron Microscope (FIB-SEM) technique for Transmission Electron Microscopy (TEM) was used to analyse the secondary mineral assemblages in the nakhlites. Fracture-filling assemblages in the nakhlites are found to be dominated by an amorphous, hydrated Fe-silicate - a ‘gel’. The gel decreases in Mgat/Mgat+Feat ratio going up the expected depth profile of the nakhlites. Other phases, especially 2:1 smectites - 1:1 phyllosilicate and carbonate are associated with the gel. Newly discovered 1:1 phyllosilicate, suggested to be serpentine, is also found in the mesostasis of Lafayette. A model is proposed describing the formation of the nakhlites’ secondary assemblages by an impact-induced hydrothermal system based on the mineralogical and geochemical differences between different samples. A suite of Stardust cometary samples have also been analysed using FIB-TEM and microfocus X-ray spectroscopy that includes: X-ray Fluorescence Spectroscopy (XRF), X-ray Absorption Near-Edge Structure (XANES) and Extended X-ray Absorption Fine Structure (EXAFS) at the Diamond synchrotron. Attempts have been made to distinguish the cometary material from that formed by capture heating in aerogel via the identification of ferric-oxides at track entrances. Finally, the mineralogy and morphology of a terminal particle from Stardust track #154 was studied by analytical TEM. The results show that Comet Wild2 contains a unique Al-diopside-bearing grain, having affinities with the minerals found in refractory objects from the inner Solar System. Upon comparison with different early Solar System materials, the grain’s mineral assemblage most closely resembles Al-rich chondrules. This adds to the refractory inventory identified in Comet 81P/Wild2.

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Abstract: Al3Ti, Al13Cr2 and Al13Fe4 are important intermetallics in a number of Al alloy systems including complex ultra-high-strength systems with excellent elevated-temperature performance. A full knowledge of their properties and crystallographic structures is a key factor for the understanding of these complex alloys. In the present study samples of the three pure intermetallics were prepared and regions of interest identified in a billet of Al93Fe3Cr2Ti2 alloys and 20 × 10 × 2 µm samples extracted utilizing a Focussed Ion Beam Transmission Electron Microscopy (FIB TEM) sample preparation technique. Using the microfocus spectroscopy beamline I18 at Diamond Light Source we were able to examine 5 µm sections of the samples using X-ray Diffraction (?-XRD) and Extended X-ray Absorption Fine Structure (?-EXAFS) in an attempt to describe the local structure of the second-phase particles and characterized the microstructure of the FIBed samples to selectively illuminate the different phases.

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Abstract: Thermal spraying is emerging as the leading route for the deposition of protective coatings onto engineering components to improve operation under extreme conditions of temperature, wear or corrosion. Detailed microstructural assessment is a key element in improving coating performance, and this study demonstrates the application of microfocus X-ray techniques to the determination of elemental and structural variations in the coatings.