Due to their high swelling ability, high water retention capacity and low permeability, compacted bentonites have been considered as a key component of cover lining systems for storage of low and medium level toxic wastes and as barrier and backfilling materials for long-term safe storage of high level toxic waste in many countries. This thesis presents an experimental, theoretical and numerical study of thermo-hydromechanical- chemical behaviour of MX80 bentonite in geotechnical applications. The determination of swelling pressures of compacted bentonites is an important aspect of most bentonitebased barrier systems. Swelling pressures of bentonites are usually determined in the laboratory under constant volume conditions using oedometers. Powdered bentonites are usually compacted in stainless steel cylindrical specimen rings and tested immediately after the compaction process is completed. The swelling pressures thus measured are influenced by some post compaction residual stresses. However, bentonites in the form of pellets and bricks are prepared and used in repository conditions that, in turn, are free from any post compaction residual stresses. The influence of post compaction residual stress on swelling pressures of compacted bentonites for a range of dry density that are of interest has not been explored in the past. Such studies are of potential interest for the safe and efficient designs of toxic waste disposal repositories. Many of the waste repositories are commissioned in locations where the ground water either contains significant amount of salts or the repositories are anticipated to receive saline water from sea. Additionally, in some cases, the wastes that are disposed emit very high temperatures (e.g. spent fuel). Under these repository conditions, compacted bentonite barriers are subjected to both thermal and hydraulic loadings at opposite boundaries. A detailed study devoted to appreciate the combined influence of an elevated temperature, bulk fluid type and solute transport due to both hydraulic and thermal gradients are necessary to better the understanding of the mechanical behaviour of compacted bentonites in many practical engineering problems. Constant volume swelling pressure tests were carried out on compacted MX80 bentonite specimens in order to study the influence of post compaction residual stress, electrolyte concentration and temperature (for isothermal conditions) on the swelling pressure. The dry density of the bentonite was varied between 1.1 to 1.9 Mg/m3 to cover a wide range of compaction conditions. Theoretical assessments of swelling pressures were made using the Gouy-Chapman diffuse double layer theory and the Stern theory, as applicable to interacting clay platelet systems. Further, the experimental and the theoretical swelling pressures were compared in order to bring out the applicability of the electrical theories in assessing swelling pressures of bentonites for both compacted saturated and initially saturated slurried conditions. A series of thermal and thermo-hydraulic tests were carried out on bentonite specimens under laboratory scale settings. During the thermal tests, temperatures of 85 and 25 °C were applied at the bottom and top ends of the specimens, respectively. During the thermo-hydraulic tests, in addition to unequal temperature at opposite ends, distilled water was supplied from the top end of the specimens. The temperature and the relative humidity were monitored along predetermined depths of the specimens during both types of testing methods. The swelling pressure variations were monitored at the opposite end of the heat source. Changes in water content, dry density and concentrations of cations and anions along predetermined depths of the specimens were measured after termination of each of the tests. A thermo-hydro-mechanical finite element simulation was undertaken specifically for swelling pressures using the numerical code COMPASS (COde for Modelling PArtially Saturated Soils). Further, the experimental and the simulated results were compared both for thermal and thermo-hydraulic boundary conditions. Compacted bentonite specimens with post compaction residual stresses exhibited lesser swelling pressures as compared to their stress released counterparts. Agreements between the calculated swelling pressures from the Stern theory and the experimental swelling pressure results were found to be reasonable for compaction dry densities of less than 1.45 Mg/m3, whereas at higher dry densities, agreements between the measured swelling pressures and those calculated from the electrical theories were found to be poor. Conversely, compressibility behaviour of initially saturated slurried bentonites was found to be captured well by the electrical theories. On account of vapour flow under thermal gradients, compacted bentonite specimens exhibited swelling pressures at the opposite end of the heat source. The measured swelling pressure for the thermal gradient adopted varied between 0.5 to 1.2 MPa, whereas greater swelling pressures were noted due to an applied thermo-hydraulic gradient. Evaporation, condensation, diffusion and advection processes influenced the distribution of ions in compacted bentonite when subjected to both thermal and thermo-hydraulic gradients. The finite element code, COMPASS, enabled assessing changes in suction and swelling pressure of compacted bentonite satisfactorily under both thermal and thermo-hydraulic hydraulic gradients.

This thesis presents work carried out to further the understanding of the use of waste Acid Mine Drainage (AMD) solids to remove phosphorus from wastewaters. AMD can result in serious pollution and so is often treated by the Coal Authority in the UK the resultant solids being a costly disposal issue. Currently the Water Framework Directive (WFD) is putting increased strain on technology used to remove phosphorus at WasteWater Treatment Works (WWTWs). The work presented in this thesis therefore investigates the use of a problematic waste to provide a novel solution to the issue of phosphorus removal at WWTWs. There has been previous work carried out on the use of both AMD solids and AMD-cement pellets to remove phosphorus from wastewaters. This thesis builds upon this work, firstly the phosphorus removal achieved by unpelletised materials studied in this thesis are compared to those studied by others through the comparison of adsorption isotherms. Mirroring other studies, the principal material studied in this thesis was then pelletised using Portland cement as a binder. Phosphorus removal by these pellets in batch tests was determined and optimised. Phosphorus removal was found to increase with a reduction in pellet size and an increase in test length up to the maximum length studied of three weeks. This increase in performance was attributed to the introduction of a calcium phosphate precipitation removal mechanism as a result of the use of cement as a binder for the pellets. This was highlighted through the correlation of phosphorus removal with a drop in calcium concentrations and pH values. It was concluded that the end product of this precipitation was hydroxyapatite. Continuous column tests were performed on the pellets, it was found that the pellets not directly involved in phosphorus removal were still having their reactivity leached out by passing water and so when these pellets became involved in removal, the columns quickly failed.

The most common technique for carbon dioxide removal from gaseous streams is amine scrubbing, a proven technology in the oil and gas industries. The use of this route in coal fired power plants is not fully understood and the likelihood of solvent degradation is high. Decreased absorption efficiency, undesirable byproducts, the environmental impact of their disposal and increased process costs are the main consequences. In this study, two experimental rigs were designed and commissioned to explore the effects of gas composition and temperature on monoethanolamine degradation. Analytical procedures to detect and quantify its major thermal and oxidative degradation products were also developed. It became apparent early on that solvent degradation, under actual plant conditions, is a slow phenomenon, thus, it was decided to focus on thermal degradation. The present study uniquely enabled the absorption/desorption behaviour of thermally degraded solvents to be evaluated. The major thermal degradation products were quantified. After 14 full absorption/stripping cycles at the presence of 16% oxygen and 15% carbon dioxide, significant concentrations of nitrites and nitrates were detected in the samples. Thermal degradation at 160 oC for 8 weeks reduced monoethanolamine concentration by almost 95%, as evidenced by the chemical analysis, but the remaining solvent retained 22% of its capacity to remove carbon dioxide. Therefore, although not fully quantified, the requirement for monoethanolamine make-up may not be quite as serious as initially believed. There is some evidence to support that the rate of thermal degradation was enhanced as carbon dioxide loading increased and a 20% higher MEA loss was determined in the samples with the rich initial molar loading. A range of degradation products were quantified that correspond to those cited in the literature. 1-(2-hydroxyethyl)-2-imidazolidinone was indicated as the most stable MEA degradation product in the degraded samples at concentrations of up to 17% v/v.

This thesis examined a range of methods for sampling soil pore water to investigate the chemistry of trace elements. In particular, the study assessed whether Rhizon samplers, centrifugation, high pressure squeezing and soil suspensions in simulated pore water can be viable approaches for obtaining representative samples of equilibrated soil pore water. Results for metal solubility and speciation were interpreted in terms of both soil morphological effects on trace metal dynamics and artefacts introduced at various stages during sample preparation and handling. The main soil used in the study was an organic-rich sandy silt from a site which has served as a sewage re-processing facility for almost a century. This soil was chosen because of its importance as a long-term repository for metal-enriched sludge applied to arable land, providing a suitable medium on which to study trace metal behaviour. Pore waters were extracted and analysed for major and trace cations and anions, pH, Dissolved Inorganic Carbon (DIC) and Dissolved Organic Carbon (DOC) at two different temperatures (5 degrees Celsius and 15 degrees Celsius), in order to evaluate the extent of bacterial activity, organic decomposition and their consequences on solute composition, during pore water extractions. Speciation was estimated from analysis of pore water chemistry using two software packages (PHREEQCi and WHAM-VI). Pore waters showed different ranges of concentration between the various methods. Different mechanisms and/or chemical reactions were involved during the different extractions; a range of processes was identified, mainly dominated by metal complexation by humus acids and redox reactions. Results revealed that the soil studied was able to partially buffer the free ion activities of the metal ions in pore water with increasing dilutions, but demonstrated virtually no ability to buffer DOC. Identification of the source (i.e. location of pore space) of water extracted was also investigated using water with different isotopic composition (18O/16O). Evidence showed that centrifugation was not able to differentiate between more and less mobile water at FC conditions, rather enhancing the mixing between the two pools of water (native and labelled) by and apparent process of 'infusion'. By contrast, Rhizon samplers appeared to sample water preferentially from the more accessible pool (extra-aggregate), which proved to have a composition showing incomplete mixing with the native water. The results also suggested that mixing of the two pools was rather fast and that was almost completely attained prior to pore water extraction. The study established that the most important factors affecting pore water chemistry during extraction are the conditions to which the samples are exposed during the extraction process. For these reasons Rhizon samplers should be used as a disposable device, and are only applicable for use in high soil moisture soil contents. In contrast, they present no 'side-effects' (providing enough equilibration time) if M2+ (free ion activity) were needed as opposed to Msol (total metal concentration in pore water), as often required in environmental studies. Centrifugation is optimal for bulk solution studies, or when homogenisation represents a key experimental point; targeted studies are also possible. Soil squeezing is subject to severe limitations in the case of prolonged extractions of biologically active soils, due to the effects of anaerobism. Squeezing should only be used for 'fast' extractions of soils. Finally, batch extractions are well suited to studies on M2+ equilibria, but more studies are needed to clarify the effect of soil: solution ratio on metal and DOC solubility.

The United Kingdom utility services are facing the challenge of "mapping the underworld" over four million kilometres of buried pipes and cables (a combination of water, sewage, gas, electricity and drainage). Having accurately mapped pipes and cables increases the efficiency of street works projects, but many existing pipes and cables were only mapped relative to other topographic map features and to varying levels of accuracy. The aim of this thesis is to research various means of improving the positional accuracy of underground utilities in built-up areas through the use of Global Navigation Satellite System (GNSS), integrated with other positioning systems such as Inertial Navigation Systems (INS) and total stations. The reliability and accuracy of the integrated system is an underpinning issue and this thesis looks at testing both current and future GNSS constellations in a controlled environment at the University of Nottingham campus. GNSS integrated with an INS in the first instance, and integrated with a total-station in the second instance, are tested using a network of established points in urban canyon environments on the campus. Several, new technologies were developed by the author including: Urban Canyon GNSS Simulation (UCGS) - a GIS tool; Multiple Step Integration Technique (MSIT) - a methodology for GNSS/INS data collection and processing; and Continuous Updating Technique (CUPT) - a software for GNSS/total-station integration. The results of different simulations provide evidence that using more than one GNSS constellation will significantly increase the availability of GNSS positions in urban canyon environments. However, position availability using the criteria of 5 or more satellites with a Position Dilution Of Precision (PDOP) value of 6 or less for centimetre level is not guaranteed 100% of the time when using GNSS alone. Considering the results of the integrated GNSS/INS system, the position availability was guaranteed 100% of the time in all environments, but the accuracy is not enough to meet utility service requirements. The best results used GNSS integrated with a total-station and showed that, in this case, position availability to a centimetre level of accuracy can be guaranteed 100% of the time in all environments.

A near-IR absorbing phthalocyanine containing alkylthio and alyklamino substituents along the periphery was determined to have optical properties that vary depending on surrounding solvent environment. Solvatochromic behavior of this novel chromophore has been characterized through UV-Vis absorbance and fluorescence spectroscopy. Conformational analysis using the B3LYP/6-31G* model indicates the lowest energy conformer with hydrogen bond like interactions between the sulfur lone pair and the hydrogen on the alkylamino substituent. TD-DFT analysis of the solvatochromic phthalocyanine and its parent molecule confirms the derivative exhibits tunable optical properties based on various solvent parameters. Chapter 1 reviews the energy crisis and the potential biological implications of near-IR absorbing phthalocyanines. In addition, a brief introduction of TD-DFT is given to further describe the computational analysis utilized herein. Chapter 2 describes the synthesis, spectroscopic studies, and computational analysis of a near-IR absorbing solvatochromic phthalocyanine derivative. Chapter 3 provides a summary of the work described in this thesis and provides future directions based on the completed research.

Submitted by Gizele Lima (gizele.lima@inpa.gov.br) on 2016-08-31T13:21:43Z No. of bitstreams: 2 Tese de Doutorado_Angela Beth Jardine.pdf: 6114980 bytes, checksum: 07a301793e0522e5fb0084e12ee425fe (MD5) license_rdf: 0 bytes, checksum: d41d8cd98f00b204e9800998ecf8427e (MD5) / Made available in DSpace on 2016-08-31T13:21:43Z (GMT). No. of bitstreams: 2 Tese de Doutorado_Angela Beth Jardine.pdf: 6114980 bytes, checksum: 07a301793e0522e5fb0084e12ee425fe (MD5) license_rdf: 0 bytes, checksum: d41d8cd98f00b204e9800998ecf8427e (MD5) Previous issue date: 2016-05-10 / Conselho Nacional de Pesquisa e Desenvolvimento Científico e Tecnológico - CNPq / Plants produce and emit a large array of volatile metabolites termed biogenic volatile organic compounds (BVOCs) as an integral part of primary and secondary metabolism. Monoterpenes are BVOCs from the largest family of plant natural products, the terpenoids. Despite orders of magnitude difference in atmospheric reactivity and great diversity in biological functioning, little is known about monoterpene speciation in tropical forests. Using thermal desorption-gas chromatography-mass spectrometry techniques, twelve volatile monoterpenes were identified and quantified in a central Amazon terra firma rainforest including the first ambient air observations of the highly reactive cis-β-ocimene and trans-β- ocimene. At the ecosystem scale, monoterpene mixing ratios in the ambient air were greatest at the top of the canopy where light and temperatures are greatest. Leaf level monoterpene emissions were found to be light dependent among the Amazon trees sampled in the field. However, during drought stress conditions that led to leaf senescence, leaf monoterpene emissions were found to be first light dependent followed by temperature dependent and an acted as an early indicator of leaf lipid peroxidation. Further, leaf monoterpene emissions revealed a strong non-linear relationship with net photosynthesis (Pn), dedicating up to 2% of Pn to monoterpene emissions at leaf temperatures up to 30ºC and continuing to rise as leaf temperatures increased. These results suggest that highly reactive monoterpenes may play important roles as antioxidants protecting photosynthesis in plants and serve as near-canopy sources of secondary organic aerosol precursors through atmospheric photooxidation reactions. / As plantas produzem e emitem uma grande variedade de metabólitos voláteis denominados compostos biogênicos orgânicos voláteis (BVOCs), como parte integrante do metabolismo primário e secundário. Monoterpenos são BVOCs de a maior família de plantas produtos naturais, os terpenóides. Apesar de diferenças das ordems de magnitude na reatividade atmosférica e grande diversidade em funcionamento biológico deles, pouco se sabe sobre a especiação dos monoterpenos em florestas tropicais. Usando tecnicas analiticas de desorpção termica-chromatografia gasosa-espetrometria (TD-GC-MS), doze monoterpenos voláteis foram identificados e quantificados numa floresta tropical de terra firma na Amazônia central, incluindo as primeiras observações no ar ambiente dos monoterpenos que são altamente reativos, cis-β-ocimeno e trans-β-ocimeno. Na escala do ecossistema, as taxas de mistura dos monoterpenos no ar ambiente foram maiores no topo do dossel onde a luz e as temperaturas são maiores. No nível das folhas, emissões dos monoterpenos foram dependente da luz para as avores foram amostradas em campo. No entanto, durante as condições de seca com estresses que levaram a senescência foliar, as emissões dos monoterpenos das folhas foram dependente primeiro da luz e depois a temperatura e agirem como um indicador da peroxidação lipídica folha. Além disso, as emissões dos monoterpenos das folhas revelou uma forte relação não-linear com fotossíntese líquida (Pn), dedicando-se a 2% do Pn para as emissões dos monoterpenos nas temperaturas das folhas até 30ºC e continuaram a aumentar com as temperaturas da folha. Estes resultados sugerem que os monoterpenos o que são altamente reativas podem ser importantes porque eles funçiõnam como antioxidantes que protegem a fotossíntese nas plantas e também podem ser fontes perto do dossel dos precursores dos aerossóis orgânicos secundários de fotooxidação na atmosfera.

As the currently available methods for recycling of valuable metals from batteries and old electronics (commonly called eWaste) are in need of improvement, this project focuses on the development of a novel valuable metals recovery method by electrolysis in molten salts. The process proposed consists of three steps: metal oxides dissolution in borate salts, liquid-liquid interface ion transfer between the borate and chloride layer, and electrodeposition from the chloride phase. Inherent borate salts stability and its affinity to metals, coupled with the chloride salts large electrochemical window enables a stable and efficient (semi)-continuous process concept to be explored. Two electrolytic cell concepts akin to an industrial set-up were designed. The first composed of three interconnected chambers each for one of the three steps of the process, or a simpler, single-vessel solution relying on the immiscibility of the molten phases. For the needs of a laboratory scale testing the smaller, one vessel solution has been assembled. The proposed recycling method is a novel solution for the recovery of valuable metals considered and evaluated in this work; Co, Cu, Ni, and Mn, present in most Li-ion and Ni-MH batteries, but also other metals suitable for electrodeposition present in the eWaste or other metal-rich waste streams. The process proposed was designed, evaluated and resulted in a successful recovery of all of the metals considered. Novel and promising experimental data on the metal oxides dissolution in molten borate salts is reported. Boron oxide salts were assessed, with the sodium borate achieving significant metals concentrations ranging from 4-20 wt%. Metals distribution between the oxide and halide layers was evaluated, and was found to be biased towards the borate layer due to its structure resulting in high metal affinity, with the metal ions concentration in the chloride layer around 1 wt% for the evaluated salts combination. This enables the sodium borate phase to work as a buffer, feeding the dissolved metal required for the electrodeposition into the chloride layer sustaining the process. Liquid-liquid interface transfer and diffusion phenomena in the melt as well as the metal electrodeposition parameters were studied using a range of (electro)-analytical methods, validating the main steps of the proposed metal recovery process. The system was evaluated in a three-electrode set-up (WE: tungsten, CE; graphite, QRE: tungsten) and the formal redox reaction potentials were reported for the following feedstock: Co2O3 [-0.733/-1.848 V], CuO [-1.297/-2.375 V], Mn2O3 [-1.552 V] and NiO [-1.734 V] versus chlorine evolution. The recovered metals were analysed and found to form high purity (~99 %) dendritic deposits (SA/V of 950 cm-1), which also supports the assumption of a diffusion controlled process. This marks the successful outcome of this proof-of-concept process, providing a feasible, alternative valuable metals recovery method design.

The results of the degradation of glycerol in supercritical water show that conversion of pure glycerol (58 % at 550 \(^0\)C) without a catalyst can be achieved, but complete conversion of pure glycerol over Fe\(_2\)O\(_3\)+Cr\(_2\)O\(_3\) or Fe\(_3\)O\(_4\) catalysts (at 550\(^0\)C, 250 barg, <15 wt% feed concentration, 10.1 g and 4 mm catalyst particles) can be reached. Crude glycerol conversion decreases from 100 to 67 mole% and 100 to 74 mole% over the same catalysts and conditions. Hydrogen yield was as high as 61 mole% and 49 mole % when crude glycerol was gasified over Fe\(_3\)O\(_4\) and Fe\(_2\)O\(_3\)+Cr\(_2\)O\(_3\), respectively. 64 mole% of syngas was obtained with minimum 4:1 mole ratio of H\(_2\):CO. Hydrocarbon yields (69 mole% for ethylene and 22 mole% for methane) were obtained and this decreased with temperature as resulted of thermal cracking. Small amounts of char (<3.1 wt%) and carbon deposition on the catalyst surface and inside the reactor wall was observed. Prolonged exposure of Fe\(_2\)O\(_3\)+Cr\(_2\)O\(_3\) to 172 h on-stream under supercritical conditions resulted in fragmentation of the surface from metal sintering, which reduced activity for H\(_2\) production. 42 mole% of hydrogen was obtained from 2 wt% digestate gasification at the same conditions.

Current food production and consumption practices are depleting natural resources and polluting ecosystems at a rate that is unsustainable and are one of the main causes of anthropogenic climate change. If this trend does not change, externalities of food production will be exacerbated in future decades due to population growth and increasing living standards. A shift towards low impact diets has been proposed as part of the solution. The public food sector offers tremendous potential for influencing such a shift; however currently in the UK this potential is only partially exploited as national guidelines for public food procurement avoid promoting the adoption of low impact menus. This doctoral research aims at addressing this shortfall by creating a procedure for the design of low impact primary school menus. This is informed by a life-cycle based tool (the Environmental Assessment Tool of School meals, EATS) that enables catering companies and local authorities to self-assess the environmental impact of a meal in terms of its carbon and water footprint, with the purpose of identifying hotspot meals and comparing alternatives in the design of new menus. The data underlying EATS includes the results of a meta-analysis of the existing literature on the carbon footprint of 110 food products commonly used in the preparation of primary school meals in the UK. To validate EATS, a statistical analysis of the underlying data was performed, feedback from its potential users was collected, three case study analyses were developed, and the results provided were compared with existing studies.