The atmospheric corrosion of 304L and 3 16L austenitic stainless steels was investigated in conditions relevant to the storage of intermediate level nuclear waste (I L W). Thin electrolyte films were created via automated droplet deposition, allowing multiple tests to be conducted in parallel. In-situ monitoring of droplet arrays on stainless steel samples was conducted with the use of a flat-bed document scanner, allowing large-scale, automated monitoring of corrosion processes. The initiation time for individual corrosion processes was established, showing that corrosion was slower to initiate under less aggressive conditions, and allowing 'true corrosion site lifetimes to be recorded, and compared with their depths. The presence of precipitated species within an electrolyte film was shown to affect the corrosion processes within that film. Both NaCl precipitates and glass shards acted as barriers to ion transport. This affected both the propagation of corrosion, and the electrochemical potential within the droplets; a higher precipitate content decreased the average corrosion depth and the extent of corrosion. The presence of nitrate and sulphate salts, both known corrosion inhibitors in full- immersion conditions, was shown to inhibit atmospheric corrosion when the inhibitor:chloride ratio was above a certain value. This was independent of the absolute amounts of salts, but dependent on the exposure humidity of the test.

Exposure to air pollution can cause adverse health effects, may also adversely affect the central nervous system and affect cognitive performance. Epidemiological studies depend on central site monitors as surrogates to assess personal exposure to air pollution, which can be inaccurate because they do not assess personal exposure in a variety of activities and microenvironments. This thesis aims to assess the level of misclassification in data from central site monitors by using portable modern sensors with high temporal resolution to characterize personal inhaled doses of BC, PM2.5, and UFP, and compare the measurements with surrogate exposure metrics. It also seeks to identify contributing activities and sources associated with the highest concentrations of the three pollutants, and to determine the contribution of these activities and microenvironments to personal exposure, and to study the impact of short-term exposure to air pollution on cognitive function. The first finding is that central site monitors are not a good surrogate for personal exposure. Secondly, travelling in vehicles is linked to the highest concentrations of the three pollutants, while other outdoors activities and outdoors commuting are linked to the highest concentrations of BC and PM2.5, cooking is linked to the highest concentrations of UFP, and activities and time spent indoors are the highest contributors to personal exposure. Thirdly, the results provide strong evidence that short-term exposure to PM2.5 from candle burning and commuting has an adverse effect on cognitive performance.

Using carbon adsorbents is the most common method of removing waste organics from water. However, the question remains of what to do with the carbon after adsorption. Landfill or incineration come with the obvious environmental consequences, and thermal regeneration is energetically costly and can be wasteful. The wastewater management company Arvia have developed a process for using electrochemical regeneration as an alternative. This thesis has examined that process in detail, in particular the role of the specific granular activated carbon used (Nyex). Nyex was characterised using a range of microscopic and spectroscopic methods. It is a highly crystalline graphite material which has been intercalated with bisulphate ions and water. It has an accessible surface area of 2.04 m2/g and a classic platy morphology with oxygen surface functionality. Additionally, the intercalation process has not changed the inter-layer distance. It is known that graphite intercalation compounds can expand upon thermal treatment. Upon heating using either an oven or a domestic microwave, Nyex expanded rapidly, resulting in an expanded carbon with a very typical vermiform morphology. The maximum expansion volume recorded for Nyex was 394 mL g 1, for microwave expanded Nyex. Surface area analysis confirmed that this volume expansion had not introduced porosity into the structure. The structure was damaged by the expansion but the overall number of defects has decreased. Analytical electrochemistry has been carried out, using Nyex as a working electrode and four test materials. Phenol can be irreversibly oxidised at a Nyex working electrode, and the build-up of breakdown products on the surface can be prevented by the application of 1.85 V for 7 s between each cyclic voltammogram. The increased surface area of expanded Nyex led currents to flow at an order of magnitude higher (approximately 40 µA compared to 5 µA for unexpanded Nyex) meaning more phenol could be oxidised at the same potentials. Humic acid and hydroquinone both showed no electrochemical activity at Nyex. Additionally, repeated cycling of potentials in hydroquinone led to the build-up of carbonaceous material on the surface of the electrode which passivated it. The industry provided test material, Tellus oil, passivated both Nyex and platinum electrodes. Two extraction methods to analyse the quantity of oil left on the Nyex after the Arvia process were developed. Using supercritical CO2 (scCO2) an extraction efficiency of 63% was achieved using 1 hour of extraction. Using acetone extraction, efficiencies in the region of 80 - 90% could be achieved in 10 min. The scCO2 extraction was complex, and required specialist equipment and training. In contrast the acetone extraction was simple and gave more reproducible results. Samples provided by Arvia from their pilot plant trial were extracted using the acetone extraction method. The concentration of oil on the samples was approximately 50 wt.% and did not decrease after 1100 hours of regeneration. A trial was run at Nottingham using 25 wt.% of oil which also did not decrease after 8 hours of regeneration. In summary, the combination of analytical electrochemistry and solvent extraction has shown Nyex is able to absorb up to 50 wt.% of oil from water, but the Arvia process does not destroy complex oily wastes. It is effective at oxidising phenol from water, with cycles of regeneration ensuring the Nyex surface is not passivated by the build-up of breakdown products. Nyex expanded in either the microwave or an oven is capable of oxidising much higher quantities of phenol because of its higher surface area.

Disposal of low level radioactive liquid waste to soil is commonly practiced. Therefore, sorption of uranium from aqueous solution and fixation of uranium into soil are processes which are crucial to the attenuation of uranium and protection of groundwater. Exposure of human populations is either by direct water consumption or through crop irrigation and transfer into the food chain. In this study a range of materials, including natural materials (e.g. biochar and the natural zeolites ‘Chabazite and Mordenite’) and the synthetic zeolite ‘Faujasite-X’, were investigated as potential adsorbents for UVI from aqueous solution. A range of experiments were carried out to investigate the efficacy of using these adsorbents to successfully adsorb and fix UVI from aqueous solutions. These included sorption and desorption experiments, quantifying time-dependent fixation of UVI and applying kinetic models of this process and measuring isotopically exchangeable UVI within adsorbent materials when possible. The factors affecting adsorption processes, such as solution pH, initially added UVI concentrations and adsorption contact time, were also investigated. Speciation of U in the solution phase was investigated using the Windermere Humic Aqueous Model (WHAM-VII). Saturation indices of potential solid phases were also configured using known solubility products and the free ion activities predicted from the speciation model, WHAM-VII. Mordenite zeolite showed a poor adsorption affinity for UVI as the solution pH was continuously buffered towards high pH values > 6.5 which favours UVI ion solubilisation as a result of uranyl carbonate complex formation. Uranium (VI) ion adsorption on chabazite at pH 4.7 at 20 oC was found to fit the Freundlich adsorption isotherm but the optimised equation parameters were unique for each contact time of 1, 5, 10, 20 and 30 days. The time-dependent fixation of UVI on chabazite was found to follow an irreversible first-order kinetic equation and an intraparticle diffusion model suggesting slow penetration of chabazite porous structure following initial surface adsorption. Isotopically exchangeable 238UVI (the E-value, UE) adsorbed on chabazite showed that > 65% of initially added UVI remained isotopically exchangeable. Faujasite-X also showed time-dependent fixation of UVI over 35 days of adsorption contact time at pH values 4, 5 and 6. The adsorption kinetics were best described by an irreversible first-order equation and a spherical diffusion model. Desorption trends showed that UVI adsorption into faujasite- X was almost wholly irreversible. Saturation indices calculated from the solubility products and free ion activities of constituent ions showed that the fixation of UVI was not controlled by the precipitation of any solid phase investigated at the studied range of pH values. Bone biochar, a by-product from the production of biofuel and syngas by gasification, was tested as a material for adsorption and fixation of UVI from aqueous solutions. A batch experiment was conducted to study the factors that influence the adsorption and time-dependent fixation on biochar at 20◦C, including pH, initial concentration of UVI and contact time. Uranium (UVI) adsorption was highly dependent on pH. However, it was found that UVI adsorption on biochar was high over a wide range of pH values, from 4.5 to 9.0, and adsorption strength was time-dependent over several days. The experimental data for pH> 7 were most effectively modelled using a Freundlich adsorption isotherm coupled to a reversible first order kinetic equation to describe the time-dependent fixation of UVI within the biochar structure. Desorption experiments showed that UVI was only sparingly desorbable from the biochar with time and isotopic dilution with 233UVI confirmed the low, and time-dependent, lability of adsorbed 238UVI. Below pH 7 the adsorption isotherm trend suggested that precipitation, rather than true adsorption, may occur. Across all pH values (4.5–9) measured saturation indices suggested precipitation was possible: autunite below pH 6.5 and swartzite, liebigite or bayleyite above pH 6.5 Another source of bone biochar with a fraction size of (20x 60 mesh) was investigated as candidate materials for soil remediation. Its ability both to adsorb uranium and to render it non-labile (i.e. chemically inactive) was tested by addition to a wide range of soils recently spiked with 238UVI and incubated under moist conditions. The overall aim was to recommend improved strategies for immobilisation of uranium in soils subject to application of low level radioactive waste solutions. Several measurements were made to assess possible reductions in U availability from biochar addition, including U solubility in 0.01 M Ca(NO3)2, exchangeability in 1 M Mg(NO3)2 solution and isotopic dilution with 233U and 236U. Results showed that 41.3 %, 27.6%, 28.9% and 31.7% were isotopically exchangeable on average for soil amended with 0%, 3%, 5% and 10% loading of biochar, but overall there appeared to be only marginal advantages in adding even large concentrations of biochar to soil. The major factor controlling U solubility, exchangeability and lability was soil pH and the pH value resulting from biochar, rather than the biochar itself. Therefore, while the use of biochar to effectively remove U from water is clear, its role in adsorbing U in the highly buffered soil environment is probably minimal.

Adsorption of heavy metal ions (e.g. copper, nickel and lead) onto sphagnum moss peat was investigated. The influence of pH, concentration, temperature, nature of solute, number of solutes simultaneously present, peat dose and reaction time on batch adsorption equilibria and kinetics tests were examined. Batch adsorption of copper and nickel onto peat was pH dependent, the optimum range being 4.0 to 5.0 for copper and 4.0 to 7.0 for nickel. Langmuir and Freundlich isotherms showed a single relationship between initial metal concentration, metal removal, and initial pH. The latter was found to control efficiency of metal removal. The use of peat in removal of lead from aqueous solution was studied in batch experiments. Investigations included the effect of pH and temperature of adsorption. The adsorption equilibria data followed Langmuir and Freundlich models. Efficiency of lead removal depended very little on the reaction temperatures (12 to 37°C) and initial pH values (4.0 to 6.0). The results suggested that the adsorption process is endothermic for lead-peat adsorption. Kinetic data suggested involvement of a chemical rate-limiting step, and a predictive relationship was derived relating metal removal to peat dose. In comparison with other metals, nickel removal is poor, and possible reasons are discussed. Kinetic results also indicated that pore diffusion is not the only rate determining step in peat metal adsorption. A rate equation is described for the study of the kinetics of adsorption of aqueous divalent metal ions onto sphagnum moss peat for a range of conditions. An empirical model was devised for predicting percentage metal ion adsorbed. The model showed a high coefficient of correlation, indicating its reasonableness. The last section describes the results of an examination into the simultaneous adsorption by peat of several metals. Initially copper and nickel from both single- and bi-solute systems were tested. In general, pore diffusion appeared to be the rate-controlling step. The effects of competitive adsorption in batch systems for copper and nickel system was also studied in various ratios of metal concentration. A mathematical model was used successfully and shown to be predictive for various ratio of metal ions concentration in competitive adsorption. The dose effect on the uptake of metals on moss peat was also studied for bi-solute adsorption systems. The best interpretation which could be placed on the data was that the behaviour of nickel was unusual. The results also showed that the kinetics of adsorption were best described by a second-order expression rather than a first-order model. For metal ions which are of different size but are divalent metal ions, we used lead(II) and copper(II) as well as lead(II) and nickel(II) systems. The effects of competitive adsorption in batch systems indicated that copper had a greater effect on lead adsorption than did nickel. However, lead had a greater effect on nickel than copper. A copper, lead and nickel triple-solute system was also tested. The adsorption of any single metal such as copper, lead and nickel was hindered by the presence of the other metals. The competitive effect appears to have affected the three ions in the order nickel > lead > copper with nickel affected most; the adsorption capacity for each solute from the mixed solution was 15.9, 57.4 and 71.5% of that of a single-solute system for copper, lead and nickel, respectively. The kinetic results showed that the heavy metals are adsorbed fairly rapidly, and that there is a relatively good fit between experimental data and the second order model for copper, lead and nickel.

Groundwater quality sampling guidance typically requires representative samples to be obtained. Such guidance is not always clear what this means and which sampling methods are most appropriate. The situation is complicated by increasing well screen/open interval length. Uncertainty, resulting particularly from observations of vertical flow in wells has led to calls for the use of long-screen (> 3 m) wells to be abandoned for groundwater quality monitoring. Here, four complementary field and modelling studies at various scales are used to examine appropriate groundwater quality sampling in such wells. Numerical modelling demonstrates that literature reported vertical flows in wells < 10 m in length are sufficient to bias pumped groundwater quality sampling. Bias starts for vertical well flow rates less than 50 % of the pumping rate. Vertical flow measurements explain differences and similarities in historical passive sampling between four boreholes and allow vertical aquifer concentration distributions to be quantified. However, such quantification requires per-borehole flow measurement. New technology (Active Distributed Temperature Sensing) provides a versatile alternative to existing borehole flow characterisation methods under ambient and pumping conditions. Data from contrasting field environments demonstrate that even without comprehensive flow investigation long-screen wells can still provide useful information about groundwater concentrations and trends.

High throughput analytical methods based on UPLC-APCI-HRMS and/or UPLC-ESI-HRMS were developed for the multi-residue analysis of pharmaceuticals, personal care products (PPCPs), brominated flame retardants (BFRs) and their degradation/transformation products. The PPCPs method was successfully applied to analysis of freshwater samples from Egypt. Target PPCPs were ubiquitous in the Egyptian aquatic environment and displayed relatively high concentrations in an effluent sample from a hospital wastewater treatment plant. The BFRs method was applied to screen for legacy BFRs, novel BFRs and their potential degradation/transformation products in simulated landfill leachate samples. In vitro bioassays were developed to study for the first time the metabolism of the novel BFRs TBECH by human liver microsomes and EH-TBB and FM550 by human skin S9 fractions. TBECH was metabolised by hepatic CYP450-mediated enzymes to produce a complex mixture of hydroxylated, debrominated and α-oxidation metabolites. EH-TBB and TPhP (in the FM550 mixture) underwent biotransformation by carboxylesterases in human skin S9 fractions. Kinetic modelling of the studied hepatic and dermal human biotransformation reactions revealed that exposure to multiple chemicals significantly influences the metabolic rates of target compounds. In vitro – in vivo extrapolations were also modelled to investigate the xenobiotic clearance capacities of human liver and skin.

No description available.

published_or_final_version / Public Administration / Master / Master of Public Administration

No description available.