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Abstract: The poorly controlled disposal of chromium ore processing residue (COPR) is a globally widespread problem due to its potential to form chromium contaminated hyperalkaline (pH > 12) leachates. These highly oxidising leachates typically contain chromium in the Cr(VI) oxidation state as its chromate anion (CrO42-). This anion is highly mobile, toxic, carcinogenic, and exhibits a high degree of bioavailability. Under reducing conditions chromium exists in the non-toxic and poorly soluble Cr(III) oxidation state. Thus, the reduction of Cr(VI) to Cr(III) is often the goal of remediative strategies. In anaerobic subsurface environments where reducing conditions are established by the indigenous microbial population, chromium reduction can occur naturally. The microbial transformation of Cr(VI) to Cr(III) can be both a result of its direct use in microbial metabolism, or through its indirect reaction with microbially produced reduced species, e.g. Fe(II). This study has used a multidisciplinary approach to investigate the biogeochemical influences on the fate and stability of Cr(VI) leaching from a site of COPR in the north of England. Reducing sediments encountered directly beneath the COPR waste were found contain elevated concentrations of chromium. These sediments were shown to be able to remove aqueous Cr(VI) from solution when incubated with contaminated site groundwater in microcosm incubation experiments. This removal is likely a result of the abiotic reduction by soil associated microbially produced Fe(II), followed by precipitation as insoluble Cr(III) hydroxides. X-ray absorption spectroscopy (XAS) and electron microscopy confirms the association of chromium as Cr(III) with iron in these soils, hosted as a mixed Cr(III)-Fe(III) oxyhydroxide phase. Upon air oxidation, only minor amounts of chromium was remobilised from these sediments as Cr(VI). A diverse population of alkaliphilic microorganisms are indigenous to this horizon, capable of successful metabolism despite elevated pH values. This population was found to contain a consortium of microorganisms capable of iron reduction when incubated at pH 9 to 9.5. Microbial community analysis found taxonomic similarity to several known metal reducing alkaliphiles from the phylum Firmicutes. These results suggest that the novel action of iron reducing alkaliphiles indigenous to reducing sediments beneath COPR sites may provide zones of natural chromium attenuation via microbially mediated mechanisms of Cr(VI) transformation.

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Abstract: There is a well-established literature indicating a relationship between iron in brain tissue and Alzheimer's disease (AD). More recently, it has become clear that AD is associated with neuroinflammatory and oxidative changes which probably result from microglial activation. In this study, we investigated the correlative changes in microglial activation, oxidative stress, and iron dysregulation in a mouse model of AD which exhibits early-stage amyloid deposition. Microfocus X-ray absorption spectroscopy analysis of intact brain tissue sections prepared from A?PP/PS1 transgenic mice revealed the presence of magnetite, a mixed-valence iron oxide, and local elevations in iron levels in tissue associated with amyloid-?-containing plaques. The evidence indicates that the expression of markers of microglial activation, CD11b and CD68, and astrocytic activation, GFAP, were increased, and were histochemically determined to be adjacent to amyloid-?-containing plaques. These findings support the contention that, in addition to glial activation and oxidative stress, iron dysregulation is an early event in AD pathology.

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Abstract: This thesis reports a study of the sulfur problem which is the production of sulfuric acid via the oxidation of iron sulfide in the timbers of the Mary Rose a flagship of Henry VIII 's navy which sunk in 1535 and was raised in 1982. The work has involved a range of chemical and physical techniques with particular use of synchrotron sources to measure the iron and sulfur speciation in the timbers with X-ray absorption spectroscopy (XAS) measurements. XAS measurements are almost unique in providing the speciation of atoms in a sample via the XANES. They are particularly useful for sulfur, which has a wide range of oxidation states. However, the current work has shown the need to use the bulk and microfocus XAS measurements in parallel, particularly for archaeological samples. It is clear that the iron and sulfur contents and speciation can vary widely from sample to sample of the Mary Rose timbers. In the study on the effectiveness of chelating agents in the removal of iron species from the timbers care was taken, wherever possible, to ensure that the same samples and sample positions were used for the before and after treatment measurements. The nature of the iron and su~ur species is of extreme importance because it is assumed that it is Fe" that gives rise to the production of su~uric acid. The current study has shown that in the timbers that had not been PEG treated contained iron in the surface regions that was predominantly Fe", similar to the findings of other workers. Most of the work in this thesis used samples close to the surface of the timbers. It was only in samples taken deep into the timbers experiments that there were significant concentrations of Fe". A range of sulfur species were found in the samples. The predominant species were reduced sulfur species, elemental sulfur and sulfate. Very little pyrite was found -in the timbers studied, but it should be noted that these timbers had not been PEG treated. Some pyrite was found in the cell walls. The present studies were predominantly on the surface regions of the timbers and the conclusion is that the bulk of the pyrite which may have been present had oxidised in the moist, oxygen containing environment in which they had been stored after recovery from the sea bed. A key finding of the present study is the co-location of iron and sulfate in the timbers. This had been suggested but had not been experimentally verified. The production of sulfuric acid in the timbers is thought to involve the oxidation of iron sulfides in the presence of water to produce is iron sulfate and sulfuric acid. The fact that the present experiments show iron and sulfate in the same positions i'] the XANES maps strongly supports the proposed oxidation mechanism of iron sulfides. The bulk and microfocus XAS experiments show that a large fraction of the iron in the current samples was in the form of an oxide. This is most likely to be goethite (FeO(OH)). The XANES analysis and the fitting of the EXAFS are consistent with this identification. All the four chelating agents used in this work (EDTA, DTPA, ammonium citrate and calcium phytate) were effective in removing iron from the timbers. However, the more efficient are DTPA and calcium phytate in terms of amount removed at fixed molarity. For samples that had been treated with PEG the current work showed that the chelating agents were less effective. This is presumably due to the PEG blocking the penetration of the solutions of the chelating agents into the wood.

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Abstract: The luminescence emission of quartz is used in optically stimulated luminescence dating (OSL), however the precise origins of the emission are unclear. A suite of quartz samples were analysed using X-ray excited optical luminescence (XEOL). Radiation dose effects were observed whereby the UV emissions (3.8 and 3.4 eV) were depleted to the benefit of the red emission (1.9–2.0 eV). Samples were excited at ?7 keV. Understanding why some quartz emit light more brightly than others will increase the efficiency and precision of OSL analyses.

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Abstract: Highly alkaline (pH 12.2) chromate contaminated leachate (990 ?mol L?1) has been entering soils below a chromite ore processing residue disposal (COPR) site for over 100 years. The soil immediately beneath the waste has a pH of 11 ? 12.5, contains 0.3 ? 0.5% (w/w) chromium, and 45 ? 75% of the microbially available iron is Fe(II). Despite elevated pH, a viable microbial consortium of Firmicutes dominated iron reducers was isolated from this COPR affected soil. Soil pH and Cr concentration decrease with distance from the waste. XAS analysis of soil samples indicated that Cr is present as a mixed Cr(III)–Fe(III) oxy-hydroxide phase, suggesting that the elevated soil Cr content is due to reductive precipitation of Cr(VI) by Fe(II). Microcosm results demonstrate the capacity of COPR affected soil to abiotically remove all Cr(VI) from the leachate within 40 days. In air oxidation experiments less than 2% of the total Cr in the soil was remobilised despite significant Fe(II) oxidation. XAS analysis after air oxidation showed no change in Cr-speciation, indicating the Cr(III)-containing phase is a stable long term host for Cr. This work suggests that reductive precipitation of Cr(VI) is an effective method of contaminant immobilisation in soils where microbially produced Fe(II) is present.