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Abstract: Reductive immobilization of uranium has been explored as a remediation strategy for the U-contaminated subsurface. Via the in-situ biostimulation of microbial processes, hexavalent U is reduced to less soluble tetravalent species which are immobilized within the sediments. Although the mineral uraninite (UO2) was initially considered the dominant product of biological reduction, non-crystalline U(IV) species (NCU(IV)) are found to be abundant in the environment, despite their greater susceptibility to oxidation and remobilization. However, it has been recently proposed that, through aging, NCU(IV) might transform into UO2, which would potentially enhance the stability of the reduced U pool. In this study, we performed column experiments to produce NCU(IV) species in a natural sediment mimicking the environmental conditions during bioremediation. Bioreduced sediments retrieved from the columns and harboring NCU(IV), were incubated in static microcosms under anoxic conditions, to allow the systematic monitoring of U coordination by X-ray absorption spectroscopy (XAS) over 12 months. XAS revealed that, under the investigated conditions, the speciation of U(IV) does not change over time. Thus, because NCU(IV) is the dominant species in the sediments, bioreduced U(IV) species remain vulnerable to oxidation and remobilization in the aqueous phase even after a 12-month aging period.

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Abstract: The Zn 1s valence-to-core (VtC) X-ray emission spectra of six ionic liquids have been measured experimentally and simulated based upon time-dependent density-functional theory (TDDFT) calculations. The seven ionic liquids were made by mixing [C8C1Im]X and Zn(II)X2 at three different ZnX2 mole fractions (0.33, 0.50 or 0.67) for X=Cl or Br, and a further ionic liquid was made by mixing [P6,6,6,14]Cl and a mole fraction of ZnCl2 of 0.33. Calculations were performed for the [ZnX4]2-, [Zn2X6]2- and [Zn4X10]2- ions to capture the expected metal complex speciation. The VtC emission spectra showed three bands arising from single electron processes that can be assigned to emission from ligand p-type orbitals, zinc d orbitals and ligand s-type orbitals. For all seven ionic liquids, the highest occupied molecular orbital arises from the ligand p orbitals, and the spectra for the different size metal complexes for the same X were found to be very similar, in terms of both relative peak intensities and peak energies. For both experiments and TDDFT calculations, there was an energy difference of 0.5 eV between the Cl-based and Br-based metal complexes for the ligand s and p orbitals, while the Zn 3d orbital energies were relatively unaffected by the identity of the ligand. The TDDFT calculations find that for the ions with symmetrically equivalent zinc atoms ([Zn2X6]2- and [Zn4X10]2-), the most appropriate core-ionised reference state has a core-hole that is localised on a single zinc atom. In this framework, the spectra for the larger ions can be viewed as a sum of spectra for the tetrahedral complex with a single zinc atom with small variations in the structure of the coordinating ligands. Since the spectra are relatively insensitive to small changes in the geometry of the ligands, this is consistent with the small variation in the spectra measured in experiment.

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Abstract: The reaction between ceria and hydrogen has been subject to numerous theoretical and experimental studies due to its importance as a catalytic material. Here we present dynamic and reversible evolution of the cerium oxidation states observed through X-ray Absorption Spectroscopy experiments in addition to the investigation of associated lattice expansion and contraction through X-ray diffraction and PDF methods. Employing a novel calculation of the temperature dependence of the Gibbs free energy through consideration of the relationship between the instantaneous thermal lattice expansion and the rate of change of the cerium oxidation state, the unusual redox chemistry is reported here. This unusual behaviour is interpreted as due to the formation of a metastable cerium oxyhydride as suggested.

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Abstract: Deep Eutectic Solvents (DES) are a recently-discovered category of potentially more sustainable alternative solvents. They are liquid eutectics formed upon the combination of various precursors, normally organic halide salts and neutral species. The most common DES is a 1:2 mixture of choline chloride:urea. DES are beginning to be used as non-aqueous alternative solvents for a variety of processes, such as synthesis of small molecules and materials, and electrodeposition. For the successful development and implementation of DES as a drop-in green solvent, it is important to build a strong fundamental understanding of the structure and properties. This will aid in the realisation of DES as ‘task-specific’ solvents which can be rationally tuned to fit the application of interest. There are several fundamental issues presently impeding the progression of the field of DES. Firstly, due to their similar properties and designer nature, DES are often presented as a sub-category of ionic liquids (ILs) though the combination of ionic and molecular species will yield a more structurally complex system, with contributions from electrostatic forces as well as H-bonding. In this thesis the structure of various DES has been explored primarily using neutron diffraction and atomistic modelling studies. These works showed evidence for a disordered and extensive H-bond network in the liquid rather than extensive ion complexation, which has important consequences for the design of chemical processes using DES. Overall, this thesis is a coherent body of independent systematic investigations into the solvent structure and solvation behaviour of DES, and synthesis of nanoparticles with wide-reaching environmental applications. We have built further upon the fundamental understanding of DES and have drawn comparison between systematic structural observations and the performance of DES in relevant applications. It is hoped that these findings will help with the onward development of DES as alternative solvents for efficient and sustainable future industrial technologies, which can make the world a cleaner place.

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Abstract: A legacy of radioactive waste has accumulated since the late 1940s and safe containment of long lived, highly radioactive waste is crucial for the future of nuclear power. A geological disposal facility (GDF) is the preferred method for the safe disposal of radioactive wastes; a multifaceted approach, using both engineered and natural barriers, to maximise the time between the breakdown of barriers and the final interaction with the environment and subsequently people. Clay is likely form an integral part of the engineered barrier system (EBS) surrounding the waste canisters in many proposed GDFs for heat generating radioactive wastes. The clay selected for this purpose would need to have the necessary physical and chemical properties to protect the waste container against corrosion and also to limit the release of radionuclides from the waste after container failure. Clays have a number of advantageous properties, such as high sorption capacity for radionuclides, small pore structure restricting microbial activity, and stability over geological time scales. Substitution of cations (Fe2+/3+, Mg2+, Al3+) into octahedral and tetrahedral (Al3+ and Si4+) sheets give a net negative charge on the clay layers giving interlayer spaces in-between; hydrated cations balance the negative charge within the interlayer space and cause the clay to swell filling surrounding gaps/cracks, avoiding advective flow, stabilizing the canister, and making diffusion the predominant transport mechanism within the barrier. A number of challenges such as heat (from the high level wastes 160 °C), with small changes being resisted further by divalent interlayer cations. gamma irradiation was shown to generate charge defects within the clay, increasing surface potential and activating redox properties (Fe); alpha irradiation showed localised amorphisation of the clay structure with long range order maintained. Maximising the ability of the clay barrier to withstand the challenges expected in the GDF environment would allow for the strengthening of public opinion and a faster, smaller (footprint), cheaper and safer GDF for high level, heat generating, radioactive wastes to be produced.