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The UK government is responsible for UK energy policy and has signalled a firm commitment to hydraulic fracturing for shale gas as part of its energy strategy. Yet, the Scottish Government imposed an indefinite moratorium on fracking in 2017. To explain this puzzling outcome, this thesis uses the Advocacy Coalition Framework to examine the Scottish unconventional oil and gas debates and demonstrate that Scotland possesses an analytically separate fracking subsystem, with its own actors and coalitions, 'nested' in a UK subsystem. The study identifies key actors, their stated beliefs, and drivers of policy change. In this thesis, I combine qualitative content analysis with the case study approach to capture the dynamic unconventional oil and gas policy process in Scotland and explain this major shift. I provide an in-depth examination of the Scottish hydraulic fracturing debates between 2011 and 2019. The timespan of eight years was enough for advocacy coalitions to emerge with relatively well-formed belief systems, and for policy learning to occur. The findings showed that the Scottish hydraulic fracturing subsystem was conditioned by multiple external events and instances of policy-learning that not only influenced the Scottish Government's final decision, but also its ability to make that decision. This study makes an original contribution to knowledge in the field of public policy by providing a longitudinal analysis of hydraulic fracturing policy development in Scotland. It also contributes to further development of the Advocacy Coalition Framework as a public policy theory by applying it in a multi-level governance context and expanding the concept of 'nestedness'.

This thesis investigates two problems in the field of volcanology by using a combination of remote sensing of volcanic gases, magma modelling and fluid dynamics. The first problem relates to gas-flow through particle-liquid suspension; with relevance for understanding the mechanism of intermittency and chemical changes in the gas composition in basaltic eruptions. The second problem centres around turbulent structures in vertical and wind-blown plumes. First, the injection of gas into a cylinder, which was filled with a water-glycerol mixture and particles, was investigated. These analogue experiments provides the framework of a model for episodic slug formations. The gas pressure at the base of the conduit is large enough to overcome the yield stress of crystal-rich magma and form gas channels within the pack. At a critical depth, the gas may displace the overlying crystal-rich plug en masse, producing a growing slug of gas. This plug becomes progressively sheared and weakened until gas enriched in the least soluble volatiles break through, causing an explosion at the surface enriched in CO2 and SO2. When the gas slug ascends, melt is drawn up in its wake, which exsolves the more soluble volatile components like HCl during passive degassing until the next explosive slug-bursting event. The second problem explores the turbulent structures of volcanic plumes. I show that it is possible to estimate volcanic water vapour fluxes with the combination of the measurement of convective structures in plumes and classical plume theory. This model predicts an estimate of H2O flux of Villarrica within 18 and 30 kg s-1 and between 130 and 270 kg s-1 for Etna, assuming the volcanic gas temperature is in the range of 500 to 900 ̊C. These estimated gas fluxes are reasonable estimations of fluxes derived from spectroscopy combined with electrochemical sensors of previous studies.

The advent of general purpose computing on graphics cards has led to significant software speedup in many fields. Designing code for GPUs, however, requires careful consideration of the underlying hardware. This thesis explores the implementation of fluid dynamics simulations featuring embedded cut cells using the CUDA programming platform. We demonstrate efficient generation and handling of geometric surface data in rectilinear computational grids. This is added to a split Euler solver to define piecewise linear cut cells describing solid surfaces in fluid flows. To reduce the memory footprint of embedded boundaries, we present a system of compressed data structures. The software is extended to run on multiple graphics cards and shows good scaling. Simulating embedded boundaries requires a description of object surfaces. We implement a fast and robust narrow band signed distance field generator for graphics cards based on the Characteristic/Scan Conversion algorithm for stereolithography files. The thesis presents an augmented approach to handle commonly occurring complex configurations and we show that the method is correct for all closed surfaces. We discuss efficient feature construction and work scheduling and demonstrate high-speed distance generation for complex geometries. At the core of our simulation implementation is a split Euler solver for high-speed flow. We present a one-dimensional method that achieves coalesced memory access and uses shared memory caching to best harness the potential of GPU hardware. Multidimensional simulations use a framework of data transposes to align data with sweep dimensions to maintain optimal memory access. Analysis of the solver shows that compute resources are used efficiently. The solver is extended to include cut cells describing solid boundaries in the domain. We present a compression and mapping method to reduce the memory footprint of the surface information. The cut cell solver is validated with different flow regimes and we simulate shock wave interaction with complex geometries to demonstrate the stability of the implementation. We conclude with multi-card parallelisation and analyse existing literature on domain segmentation and GPU communication. We present a system of domain splitting and message passing with overlapping compute and communication streams. A comparison of naïve and GPU-aware Open MPI shows the benefits of using CUDA specific library calls. The complete software pipeline demonstrates good scaling for up to thirty-two cards on a GPU cluster.

The research identifies fiscal terms of Production Sharing Contract (PSC) applied to Coal Bed Methane (CBM) in Indonesia and modifying these using comparative examples of the U.S. Royalty/Tax (R/T) System and the Australian Petroleum Resource Rent Tax (PRRT). This research examines the issues of CBM development in Indonesia from the Government of Indonesia (GoI) perspective, investors’ perspectives, consultancies and local community perspectives. This research involved both primary and secondary data collections. For the primary data collection, the researcher conducted interviews, focus group discussions, and local community surveys to identify the issues of CBM development in Indonesia, as well as obtaining data from government official websites. This thesis also underlines the importance of the local community role in project sustainability and directly engaged with the local communities. Meanwhile, for the secondary data collection, the researcher obtained data from various sources, such as academic journals, professional and consultancy reports, presentation slides available online, official website of some organisations, and books. This research analysed both primary and secondary data qualitatively and quantitatively. The researcher conducted the qualitative analysis mainly by using NVivo software, and the quantitative analysis mainly by using Microsoft Excel. This research is significant since it compares CBM cost structures and fiscal regimes of three different countries and hence provides as a research contribution this comparative analysis. There are three main conclusions in this research. First, the issues related to CBM development in Indonesia are interconnected one to another. These issues cannot be identified and addressed separately. Second, the main issue relies on GoI, which is the implementation of the government paradigm (Government Regulation No. 79/2014). The GoI should reconsider and reassess the implementation of their paradigm. The paradigm mentions that energy sources should no longer be taken as commodity but for the national engine of growth. Third, there are some fiscal terms that Indonesia could adapt from the U.S. and Australia fiscal systems that could address the issues being identified and create more attractive fiscal regimes for CBM in Indonesia. These are the implementation of the investment credit and ring fence policy in Australia, shared royalty implementation and local tax in the U.S. Finally, this research has contributed to the academic literature and practitioner perspectives on specific issues related to CBM development in Indonesia. The result has contributed to new knowledge on how the technical and geological conditions can influence the costs of CBM projects. This thesis has applied the interdisciplinary approach of economics and law as well as geology. This research advances lessons from the current fiscal regimes of Royalty/Tax system in Wyoming, and the PRRT system in Queensland. The suggested terms to be adopted address the current challenges which are related to each other. This is part of the international context that can be adopted to the national context, i.e. Indonesia.

This thesis is an ethnographic study of life with oil and gas in Hammerfest, the first petroleum town in Finnmark, and of what role this town plays and is cast as in narratives of petroleum as a driver for development in the larger region. It examines how oil in the Barents region is both disputed and celebrated, and how this resource, which has been central to the Norwegian economy and society for the last 50 years, is understood from northern perspectives. In particular, it explores what forms consent and conflict take, and how different actors engage in showing, masking and performing these. Throughout the thesis, I employ performance as a trope to understand the creation and circulation of narratives about petroleum in the north, and how they are put in motion by industry players, local and national politicians, environmentalists and other actors. Working in a region that is simultaneously Sápmi and Northern Norway, the thesis also asks how assimilation policies and coloniality continue to have an impact today, and how this partakes in the making of pasts, presents and futures in the region. The first part of the thesis seeks to ground the making of narratives and lives in Hammerfest, to understand how the stakes and impacts of resource development are understood locally, and how futures are made and broken by the materialisation of the petroleum projects on- and offshore. The second part of the thesis is concerned with how the industry, the state and environmentalists creatively engage with conference settings, state rituals and the legal system, to strengthen their own narrative or contest that of others. From platform openings to announcement of licensing rounds, industry celebrations to Norway's first climate lawsuit, the thesis argues that an explicit focus on performance and rituals of state and industry is critical for our understanding of industrial development and resource futures.

Determining the thermal alteration (maturity) of organic matter (OM) in sedimentary rocks is vital for predicting hydrocarbon (HC) generation and to calibrate basin models that help petroleum geologists delineate areas of interest for HC exploration. Vitrinite reflectance (VR) is the 'gold standard', however uncertainty can arise in certain circumstances, such as in rocks with sparse vitrinite particles, hydrogen-rich OM and from overpressured basins, plus issues relating to sample preparation and operator inexperience. VR is also limited to post-Silurian rocks. It is therefore essential to have a wide range of maturity methods available that an operator can call upon depending on the circumstances. This study demonstrates that Raman spectroscopy is a viable rapid and non-destructive technique to determine OM maturity that requires minimal sample preparation for coals and mudrocks. A new standard acquisition and processing method is described that is rapid and introduces less bias than previous methodologies, as spectral deconvolution is not performed. The method includes performing a Savitzky-Golay smoothing filter using a 21-point quadratic polynomial algorithm, a 3rd-order polynomial baseline correction, followed by normalizing all spectra to a maximum G-band height of 2000 au. An automated spreadsheet is presented that automatically calculates the most commonly used Raman parameters including the G-band full-width at half-maximum (G-FWHM), Raman band separation (RBS), R1 (height ratio of the D1- and G-band) and a new parameter termed the scaled spectrum area (SSA; total area between 1100-1700 cm-1). The method has been tested successfully on a suite of prospective shale gas Carboniferous rocks from the UK with a wide maturity range and has been calibrated with VR. The G-FWHM is the most reliable Raman parameter with a strong correlation with VR (R2 0.96), followed by the SSA (R2 0.88); R1 (R2 0.73) and RBS (R2 0.65). The method has been extended to characterise a suite of shale gas geological reference materials from the United States Geological Survey (USGS) and Jurassic-Cretaceous mudrock samples from the UK and Norwegian continental shelf. It is shown that isolating the organic matter using mineral acids alters the Raman parameters by reducing/removing background fluorescence caused by the non-organic components of the rock. This reduces the bias associated with background subtraction, improving precision and accuracy. Results on samples with known VR retardation due to overpressure demonstrate that Raman may be insensitive to the retardation effect. A portable Raman instrument has also been tested on a set of coal and shale rock-chips samples. The results demonstrate that the portable Raman is more suited to coal samples, as the shale samples have considerable background fluorescence which obscures the OM Raman bands, as well as increasing the bias associated with the background subtraction. A comparison of maturity results from Raman, VR, Rock-Eval (Tmax and production index) and illite crystallinity, illustrate that discrepancies can occur due to technical, methodological and theoretical issues and further supports the consensus that multiple maturity parameters should be used in order reduce the risk in estimating the maturity of source rocks. Raman is a viable alternative method to determine the maturity of OM for HC exploration, but this study highlights the pitfalls and advantages of differing Raman methodologies. It is essential that the analytical community develops a standard approach for the method to be more widely adopted in the future.

The production from an oil reservoir is a mixture of liquids (oil and water) and gas, and is often maintained by using a pump placed in the well to ensure a continuous flow to the surface. Electrical Submersible Pumps consist of stacked centrifugal pump stages, each comprising a bladed impeller (rotating part) and diffuser (stationary part). In multiphase conditions, the gas tends to accumulate in the impeller, severely reducing the pressure produced by the pump. Radial-flow pumps operate in a plane perpendicular to their rotation axis, while mixed-flow pumps are characterised by a lower meridional angle (generally 40 to 80 degrees), and are generally better at handling gas-liquid mixtures. We first describe the impact of gas on the whole pumping system, from the reservoir to the storage facility, and give context to the subject. The available literature shows that the size of the gas bubbles present in the fluid is critical to the pump performance. A transparent, full-scale pump was built in order to explore the flow features in single and multiphase flows. Laser Doppler Velocimetry and high speed imaging in single phase flow showed a high turbulence level in the wake of the impeller blades, and recirculation cells at low flow rates. In gas-liquid conditions, we demonstrated that the bubble size varies within a pump stage, as break-up occurs at the impeller tip, and coalescence is dominant in the diffuser, especially because of recirculation. The first impeller acted as a mixer, and at moderate to high gas fractions (10 to 30%), the flow patterns at the stage level alternated between bubbly and radially separated flows. Finally, a dispersed-gas model was developed to predict the pressure rise in a mixed-flow pump impeller under gas-liquid conditions. This model based on the forces acting on a single spherical gas bubble, was implemented with a simplified, parametric representation of the flow field in a mixed-flow impeller. In the meridional direction, the Coriolis force opposes the centrifugal force and the adverse pressure gradient. Both forces tend to retain the gas bubble within the impeller. The relative magnitude of the drag force strongly depends on the maximal bubble diameter, which was determined as a function of the flow conditions and used to calculate the gas velocity through the impeller. This method resulted in a better agreement with the experimental data than a one-dimensional two-fluid model where the gas phase follows the same path as the liquid. We used the dispersed-gas model to give quantitative evidence that low blade and meridional angles reduce the gas accumulation and the associated performance degradation.

Naturally occurring radioactive material (NORM) is a common feature in North Sea oil and gas production offshore but, to date, has been reported from only one production site onshore in the United Kingdom. This site, Wytch Farm on the Dorset coast, revealed high activity concentrations of lead-210 in metallic form but little evidence of radium accumulation. NORM has now been discovered at two further onshore sites in the East Midlands region of the UK. The material has been characterised in terms of its mineralogy, bulk composition and disequilibrium in the natural uranium and thorium series decay chains. In contrast to Wytch Farm, scale and sludge samples from the East Midlands were found to contain elevated levels of radium and radioactive progeny associated with crystalline strontiobarite. The highest radium-226 and radium-228 activity concentrations found in scale samples were 132 and 60 Bq/g, with mean values of 86 and 40 Bq/g respectively, somewhat higher than the mean for the North Sea and well above national exemption levels for landfill disposal. The two East Midlands sites exhibited similar levels of radioactivity. Scanning electron microscope imaging shows the presence of tabular, idiomorphic and acicular strontiobarite crystals with elemental mapping confirming that barium and strontium are co-located throughout the scale. Bulk compositional data show a corresponding correlation between barium-strontium concentrations and radium activity. Scales and sludge were dated using the 226Ra/210Pb method giving mean ages of 2.2 and 3.7 years, respectively. The results demonstrate clearly that these NORM deposits, with significant radium activity, can form over a very short period of time. Although the production sites studied here are involved in conventional oil recovery, the findings have direct relevance should hydraulic fracturing or fracking for shale gas be pursued in the East Midlands oilfield. Highly saline flowback fluid containing above regulation levels of radium has already been observed as a result of exploratory fracking operations in the North West s Bowland Shale and now appears a likely outcome if similar operations are conducted in the East Midlands. Barite (barium sulphate) coprecipitation is a cost-effective method for removing radium from solution. For the first time, reagent quantities for radium recovery by barite coprecipitation have been optimised in saline solutions of ionic strength (IS) 0.3 and 3 M. The process is highly effective, removing a maximum of ~90% radium in a single optimised coprecipitation step, but requiring substantially more sulphate at 3 M than at 0.3 M ionic strength to reach this maximum. It has been shown that, if left, the radiobarite precipitate will continue to remove radium by post-precipitation (recrystallisation). A pattern of diminishing returns in radium recovery by post- precipitation at each IS was observed; the rate was faster in the first 24 hours then dropped significantly over 14 days. After 14 days >80% of the radium was recovered, slightly more radium being removed at IS = 0.3 M. Therefore, if >90% radium recovery is sought, further co- and post-precipitation steps could be undertaken to approach the UK s 0.01 Bq/dm3 radium aqueous waste discharge exemption limit. However, compliance with UK s aqueous waste regulations would require multiple coprecipitation steps to recover >99.9% radium, which may not be feasible in practice. The Bowland Shale has high shale gas prospectivity and may be subject to further fracking operations in the future. Should local groundwaters mix with flowback fluid, there is potential for drinking water supplies to become contaminated. Baseline monitoring of groundwater was conducted in the region, so that comparisons may be made following potential fracking operations. The determined mean baseline for radium-226 and uranium-238 were 15.5 and 11.1 mBq/dm3 respectively, both below their respective notifiable drinking water level in the UK. In the majority of the groundwaters, barite is supersaturated and geochemical modelling has shown that a considerable proportion of the aqueous radium could precipitate in the Ba1-xRaxSO4 solid solution. A further increase in dissolved radium, barium and sulphate as a result of fracking will greatly increase the likelihood of concentrating the radium in barite scales, commonly found in oil and gas production equipment. What this means in terms of the potential NORM inventory is that Ra-containing NORM could manifest itself as fluid or solid waste.

The oil and gas industry in Libya has suffered a number of health and safety accidents including environmental disasters due to the nature of the work involved and the hazardous materials it handles in all facets of exploration and production. Such issues have hitherto not received due attention by the Libyan Authorities. The fact that strict HSE assessment standards are neither well-defined nor established in Libya is not helpful. Furthermore, oil and gas industry in new free Libya has suffered immensely during the 2011 Arab Spring and its rebuilding poses a number of critical HSE challenges. The purpose of the research is to develop and validate a HSE Performance Review Methodology for Libyan oil and gas industry based on clearly defined and measurable aspects for assessment. The thesis starts by performing a comprehensive literature review on all aspects of HSE including universal standards. The review indicates that there is a gap in respect of semi-qualitative methods for assessing HSE performance commensurate with other disciplines. The thesis then identifies four key research problems in the context of Libyan oil and gas industries. Based on these problems, an empirical research was conducted and included three distinct Stages. Stage 1 consisted of a pilot study based on an interview questionnaire with 15 experienced HSE professionals working in oil and gas companies in Libya to help identify key issues pertaining to HSE assessment. Data analysis results for Stage 2 have been used to derive a list of 12 main groups of HSE questions which have then been tested on 84 HSE professionals working in Libya stemming from 35 medium and large oil and gas companies. Modal distribution analyses have been performed to scope down the number of HSE performance factors, which would then be used in Stage 3 of the empirical research. This consisted of issuing the same 84 interviewees with a questionnaire requesting their assessment of how Critical, Important and Less Important were the 60 factors identified. Central Tendency, Variation Ratios and Indices of Diversity were used to successfully analyse the data. With the QAA Subject Review in mind as a potential model for the sought methodology, and a mapping of the four research problems with data analysis results from Stages 1, 2 and 3; six HSE Performance Review Aspects emerged: Prevention, Surveillance, Response, Achievements, Resource and HSE Management and Enhancement – judged and graded using a 1 to 4 scale. The HSE Performance Review methodology has been validated by direct application to five comprehensive studies starting from the self-assessment document written by the companies, an extensive review visit by peer-assessors and a final report showing grades, benchmarks and shortcomings. Lessons learned from the validation exercise have been used to revise the definition of the six Aspects and used to propose an appropriate implementation plan in Libya. The results of the validation exercise are very encouraging and readily confirm that the methodology can be applied to other industry sectors.

There were three main driving forces behind this thesis: global concern over climate change mainly due to uncontrolled carbon dioxide (CO2) emissions, the excitement over the discovery of graphene and its versatile potential, and the potential to design three-dimensional (3D) or two-dimensional (2D) structures, in our case using unique triptycene molecule. We examined two polymeric materials for CO2 adsorption and suggested simple design of disordered carbons suitable for gas adsorption studies. The approach in each task was to examine structural and adsorption properties of materials using detailed atomistic modelling employing Monte Carlo and Molecular Dynamics techniques and where possible provide experimental measurements to validate the simulations. The thesis is presented as a collection of papers and the work can be divided into three independent projects. The aim of the first project is to utilize graphene as an additive in polymer composites in order to increase separation between the polymer chains increasing available surface area. The matrix used is a polymer of intrinsic microporosity (PIM-1), which possess large surface area and narrow nano-sized ( > 2nm) pore distribution attractive for gas separation membrane applications. Adding a filler can reduce aging of the polymer, and enhance permeability across the membrane, often to the expense of loosing selectivity. Therefore, we investigated the packing of PIM-1 chains in presence of discrete 2D graphene platelets and 3D graphene-derived structures and its effect on composite structure and adsorption properties. We found that additives do not alter structural polymer properties at the molecular level preserving the same adsorption capacity and affinity. Potential permeability increase would benefit from the retention of selectivity in the material. Building on design philosophy of materials with intrinsic microporosity we continued further investigation of 3D graphene-derived structures. The idea is that highly concave molecules or polymer chains pack inefficiently creating microporous materials with sufficient surface area for gas adsorption. 3D propeller-like structures were derived from graphene arms connected through the rigid triptycene and other types of cores. The resulting structures created a large amount of micropores and showed similar CO2/CH4 selectivity to activated carbons reported in the literature. It was shown that rigid triptycene core leads to more open structures. The model was also applied to model commercially available activated carbon to predict n- perfluorohexane adsorption. The fitting to experimental structural information proved to be challenging due to trial and error nature of the approach. Nevertheless, the simple packing procedure and diverse structure design have a great potential to serve as a virtual model for porous carbons that possess pore complexity and does not require any previous experimental data to be build on. The last project concerns CO2 adsorption and selectivity over CH4 and N2 in recently reported triptycene-based polymer. The triptycene shape polymer can form a porous 2D network that can be exfoliated into free-standing sheets and potentially used as a membrane. Sheets stack in the bulk material forming anisotropic channel pores. Additionally it contains fluoro- functional groups, which are known to have a high CO2 affinity. We explored pore structure and chemistry of stacked material for gas adsorption and predicted comparable capacity and CO2 selectivity to other microporous covalent materials such as activated carbons and PIMs. The CH4/N2 selectivity was similar to currently most selective material belonging to MOF family. We showed that fluoro-group have a positive effect on CO2 affinity, however predictions are sensitive to the charges of fluorine atoms assigned by different methods.

Affordability of energy in the domestic sector is the product of three interrelated factors - level of household income, level of energy bills (which are a product of prices and levels of energy demand, mediated by tariffs and the retail market), and the amount of energy that a household needs to maintain a healthy living environment. This thesis focusses on the factors of affordability which are most relevant to the energy policy which are energy bills and energy efficiency, both of which are considered in the context of household income. Affordability of energy in Great Britain is important for separate, but over-lapping reasons. Firstly, it has important political impacts - as energy prices continue to rise, energy is repeatedly highlighted as one of the biggest financial concerns for households (uSwitch, 2013; YouGov, 2015; DECC, 2014f), leading affordability of energy to become an increasingly political issue (Lockwood, 2016). Secondly, affordability of energy has social implications which stem from the fact that the impact of rising energy bills is felt particularly strongly by those on low incomes and in inefficient homes – the fuel poor. In spite of it being twenty-five years since Brenda Boardman published her first book defining the issue of fuel poverty (Boardman, 1991), millions of households in Great Britain today still cannot afford adequate amounts of energy. This is significant because being able to afford access to basic levels of energy services such as warmth and light is essential for maintaining physical and mental health (Harrington et al., 2005; Stockton and Campbell, 2011). Thirdly, affordability has important implications for design of the energy system –a system focussed on minimising long-term costs, both through micro-scale features such as efficient network revenue regulation which keep costs down on a year-by-year basis, and macro-scale aspects such as through the development of a low-demand, highly flexible energy system which has the potential to bring costs down in the long term (Sanders et al., 2016), is likely to differ from one which in which affordability is less of a focus, or only a focus over the short term. This thesis responds to a gap in the literature in relation to the role that governance plays in affecting levels of affordability of energy for domestic consumers in Great Britain. It examines the impact of governance on energy prices and tariffs, and the impact of governance on energy efficiency of the housing stock in Great Britain. Both of these are examined in the context of levels of household income. Greater insight is gained by examining the impact of the energy governance structure in Denmark on Danish domestic energy efficiency standards, which are widely accepted to be very good (IEA, 2011). 7 This thesis makes use of existing academic and policy literature in tandem with data from fifty-six interviews with individuals from across the energy sectors in Great Britain and Denmark. The governance structure of energy in Great Britain is shown to be, on balance, not supportive of delivering affordable energy to domestic consumers. A number of specific issues within the current governance structure in Great Britain are identified. These include the presence of a limiting narrative, whereby policymakers consider affordability to be achieved principally through delivery of low prices; insufficient institutional capacity within OFGEM to keep network prices low, and monitor suppliers’ costs and profits; lack of wholesale market transparency; an anti-interventionist ideology leading to weak energy efficiency requirements for new-build and private rental properties; suppliers as poor executors of energy efficiency policy; weak demand-side interests; tariffs designed around the needs of suppliers, not consumers; an over-reliance on an uncompetitive retail market; a lack of institutional capacity amongst policy makers regarding energy efficiency, and network regulation; and weak consumer representation. A number of recommendations are put forward, including the fostering of a new narrative centred on energy efficiency; the redesign of tariffs to better protect the interests of consumers; the reallocation of responsibility for energy efficiency to local authorities; the development of greater institutional capacity among policymakers; the support for a more interventionist ideology supporting use of regulation; financial support for energy efficiency retrofit; the fostering of greater policy stability; development of new tariff structures; and the formation of a new consumer representative. Overall this thesis demonstrates that affordability of energy in unlikely to be delivered to domestic consumers in Great Britain unless significant changes are made to the governance structure of the energy sector.

There is much interest in the protection of the ecosystem within the oil and gas industry. This is particularly significant in the countries of the Middle East where the oil and gas sectors contribute a large part, in some cases all of the country economies. A case study research analysis into the Lean and Green principles of one of the State of Kuwait organisations could offer the country huge potential and could benefit other Arabian Gulf countries. In the chosen country (Kuwait), Kuwait Oil Company (KOC) has no other outlet for its business apart from oil and gas production. It also does not concern itself with other support business that could contribute to Kuwait's economy.

The metabolism of androgenic anabolic steroids has been studied in the racing greyhound. Various drug preparations have been investigated utilising different derivatisation techniques, coupled with gas chromatographic analysis, to enable the identification of key metabolites in canine post administration samples. This has led to an increased understanding of some of the generic routes of steroid metabolism that take place in the greyhound. This valuable information can help to support metabolism studies in the future. The identification of specific metabolites for each compound investigated, has provided a means for controlling the misuse of these compounds, and contributed valuable enhancements to screening protocols utilised in the canine sports drug testing industry. Utilisation of the techniques described, resulted in the identification of specific major metabolites of the anabolic steroid methyltestosterone, namely 17??-methyl-5??- androstan-3??-17??-diol and 17??-methyl-5??-androstan-3??,16??,17??-triol. 16??- hydroxylation was shown to be a major phase I metabolic pathway in the canine along with phase II conjugation with glucuronic acid. Similar results were obtained during the metabolism study of the progestatgenic steroid norethisterone. Several di- and trihydroxy metabolites were detected in the glucuronic acid fraction of the post administration urines from this study. The norethisterone metabolism study also provided some insight, into the area of trace contaminants of pharmaceutical preparations. Low levels of nandrolone metabolites were also detected in the norethisterone post administration urine samples, leading to the discovery that the administered pharmaceutical tablets contained small quantities of nandrolone and 19- norandrostenedione, albeit below FDA approved contaminant levels. Modern methods of drug screening employ such highly sensitive techniques, that they allow for the detection of metabolites of such trace contaminants, following administration of the drug preparation to the greyhound. It is therefore important to have a broad understanding of the metabolism of various drug preparations, both banned and permitted substances alike; as detection of a trace amount of a banned substance metabolite, arising from the administration of a permitted medication, whose iii metabolite profile is unknown, and therefore potentially not detected, could present an interesting case. In conjunction with research into controlling the use of banned substances for the purposes of suppressing oestrus in the greyhound bitch, an investigation into normal/reference levels of endogenous hormones has been carried out. The endogenous steroid levels in a population of 212 greyhound bitches have been studied with a view to establishing a method for the detection of the exogenous administration of the endogenous anabolic steroid testosterone. The major urinary metabolites investigated were epiandrosterone, 5??-androstane-3??,17??-diol and 5??-androstane-3??,17??-diol. Statistical evaluations have been carried out to support the implementation of a suitable threshold for the key testosterone metabolites, namely 5??-androstane-3??,17??-diol and epiandrosterone. The detection of 5??-androstane-3??,17??-diol was found to be a very good indicator of the exogenous administration of testosterone to the greyhound bitch, when compared with the reference population data for this metabolite. However, further statistical/analytical data evaluation was deemed necessary before an absolute threshold could be implemented for this analyte, for the purposes of controlling the misuse of testosterone in the racing greyhound bitch. To support the understanding of endogenous steroid levels in the female greyhound, yet further, the endogenous reproductive steroid profiles were measured throughout the entire oestrus cycle of a cohort of 33 racing bitches. The results of the study clearly indicate a surge in androgen metabolites during the first 7-10 days of the oestrus cycle, in particular epiandrosterone and 5??-androstane-3??,17??-diol. This unique set of data has provided detailed information regarding the fluctuating concentrations of androgen and progesterone metabolites (following ovulation), at key stages of the canine oestrus cycle. The information obtained from this research can be used to support regulatory decisions regarding the misuse of testosterone in the racing greyhound bitch.

Amperometric gas sensors are widely used for environmental and industrial monitoring. They are sensitive and cheap but suffer from some significant limitations. The aim of the work undertaken in this thesis is the development of ‘intelligent’ gas sensors to overcome some of these limitations. Overall the thesis shows the value of ionic liquids as potential solvents for gas sensors, overcoming issues of solvent volatility and providing a wide potential range for electrochemical measurements. Methods have been developed for sensitive amperometry, the tuning of potentials and especially proof-of-concept (patents Publication numbers: WO2013140140 A3 and WO2014020347 A1) in respect of the intelligent self-monitoring of temperature and humidity by RTIL based sensors. Designs for practical electrodes are also proposed. The specific content is as follows. Chapter 1 outlines the fundamental principles of electrochemistry which are of importance for the reading of this thesis. Chapter 2 reviews the history and modern amperometric gas sensors. Limitations of present electrochemical approaches are critically established. Micro-electrodes and Room Temperature Ionic Liquids (RTILs) are also introduced in this chapter. Chapter 4 is focused on the study of analysing chronoamperometry using the Shoup and Szabo equation to simultaneously determine the values of concentration and diffusion coefficient of dissolved analytes in both non-aqueous and RTIL media. A method to optimise the chronoamperometric conditions is demonstrated. This provides an essential experimental basis for IL based gas sensor. Chapter 5 demonstrates how the oxidation potential of ferrocene can be tuned by changing the anionic component of room temperature ionic liquids. This ability to tune redox potentials has genetic value in gas sensing. Chapters 6 and 7 describe two novel patented approaches to monitor the local environment for amperometric gas detection. In Chapter 6, an in-situ voltammetric ‘thermometer’ is incorporated into an amperometric oxygen sensing system. The local temperature is measured by the formal potential difference of two redox couples. A simultaneous temperature and humidity sensor is reported in Chapter 7. This sensor shows advantageous features where the temperature sensor is humidity independent and vice versa. The Shoup and Szabo analysis (Chapter 4) requires ‘simple’ electron transfer and as such the reduction of oxygen in wet RTILs can be complicated by dissolved water. Chapter 8 proposes a method to stop oxygen reduction at the one electron transfer stage under humid conditions by using phosphonium based RTILs to ‘trap’ the intermediate superoxide ions. Chapters 9 and 10 report the fabrication of low cost disposable electrodes of various geometries and of different materials. The suitability of these electrode for use as working electrodes for electrochemical experiments in aqueous, non-aqueous and RTIL media is demonstrated. Their capability to be used as working probes for amperometric gas sensing systems is discussed.

Holographic sensors are photonic layered structures contained in analyte sensitive lms that upon illumination produce monochromatic reflections (λ). The present work reports the fabrication of oxygen and ammonia sensors in Nafi on membranes and hydrocarbon and volatile organic compound sensors in poly(dimethylsiloxane) (PDMS) films. A holographic recording technique was developed to suit these materials consisting of the in situ formation of nanoparticles of 18nm average diameter and their subsequent ordered ablation with a 300mJ laser. The wavelength of the monochromatic reflections depends principally on the refractive index of the resulting layers (n) and the separation between them (Λ). Changes in these parameters are generated by the analyte-sensor interactions and their magnitude can be correlated to the analyte concentration. The strength of these interactions is determined by the thermodynamic properties of the analytes, such as the cohesive energy density (δ^2), and this, was coupled with a photonic model for the prediction of the holographic response. After exposure to different concentrations of the analytes, the kinetics of the responses were determined and the lowest detection limits (LDL) established as follows: Hydrocarbons in PDMS holograms 1% (v/v) in 3s for a range of concentrations from 0-100%; ammonia in Nafi on holograms 0.16% in 100s in the 0-12.5% range; the LDL for oxygen sensing could not be determined although the response was recorded down to 12.5% and up to 100% in 100s. Holographic sensors show competitive responses comparable to commercially available gas sensors for biomedical diagnostics and industrial process monitoring because of their facile fabrication and their shared sensing platform allowing multiplexing.

The mammalian spinal cord contains the neuronal circuitry necessary to generate rhythmic locomotor activity in the absence of inputs from the higher brain centre or sensory system. This circuitry is regulated by local neuromodulatory inputs, which can adjust the strength and timing of locomotor output. The free radical gas nitric oxide has been shown to act as an important neuromodulator of spinal circuits, which control locomotion in other vertebrate models such as the tadpole and lamprey. Despite this, the involvement of the NO-mediated soluble guanylate cyclase/cyclic guanosine monophosphate secondary messenger-signalling pathway (NO/sGC/cGMP) in mammalian locomotion has largely been under-investigated. The NADPH diaphorase histochemical reaction was used to identify sources of NO in the lumbar spinal cord. The largest population NADPH diaphorase reactive neurons were located in the dorsal horn, followed by the laminae of the ventral horn, particularly around the central canal (lamina X) and lamina VII. NADPH diaphorase reactive neurons were found along a rostrocaudal gradient between lumbar segments L1 to L5. These results show that that discrete neuronal sources of NO are present in the developing mouse spinal cord, and that these cells increase in number during the developmental period postnatal day P1 – P12. NADPH diaphorase was subsequently used to identify NADPH diaphorase reactive neurons at P12 in the mouse model of ALS using the SODG93A transgenic mouse. Physiological recordings of ventral root output were made to assess the contribution of NO to the regulation induced rhythmic fictive locomotion in the in vitro isolated spinal cord preparation. Exogenous NO inhibits central pattern generator (CPG) output while facilitating and inhibiting motor neuron output at low and high concentrations respectively. Removal of endogenous NO increases CPG output while decreasing motor neuron output and these effects are mediated by cGMP. These data suggest that an endogenous tone of NO is involved in the regulation of fictive locomotion and that this involves the NO/sGC/cGMP pathway. Intracellular recordings from presumed motor neurons and a heterogeneous, unidentified sample of interneurons shows that NO modulates the intrinsic properties of spinal neurons. These data suggest that the net effect of NO appears to be a reduction in motor neuron excitability.

Ukraine’s foreign policy has puzzled observers since the dissolution of the Soviet Union due to its unusual inconsistency. This inconsistency exhibited itself in contradictory decisions by the Ukrainian executive carried out within a short period of time, which signalled either greater cooperation with Russia and relative cooling of relations with the West, or integration into Western institutions and worsening of the relations with Moscow. This study aims to explain the inconsistency by examining the sources of Ukraine’s foreign policy through process-tracing in four policy cases: Ukraine’s renouncement of nuclear weapons (1991-1994), the status of the Black Sea Fleet (1991-1997), the Odesa-Brody pipeline (2002-2004), and the 2006-2009 gas disputes. Contrary to dominant interpretations of Ukraine’s foreign policy vacillation that emphasise the role of external influences, especially that of Russia and the West, this study concludes that Ukraine’s inconsistent foreign policy decisions are best explained by domestic factors – intra-executive divisions and the influence of vested interests on policy-making. The work relies on the use of primary sources including archival research, elite interviews, and Ukrainian and Russian newspaper reports.

This thesis presents work examining the characteristics and applicability of quantum cascade lasers. An introduction is given explaining both the desire for a widely tunable, narrow bandwidth device working in the midinfrared, as well as detailing the ways in which quantum cascade lasers (QCLs) fulfill these requirements. The development and manufacture of QCLs are then discussed. The experimental section of this thesis is then split into three parts. Chapter 2 concerns the characterisation and application of several pulsed QCLs. The intrapulse mode of operation is employed and the effect of the resulting rapid frequency chirp upon molecular spectra is investigated in the form of rapid passage signals. The evolution of said rapid passage signals is then investigated as a function of chromophore pressure and identity, with different QCLs, chirp rates, and optical path lengths. The prospect of producing population transfer with chirped lasers is discussed. Chapters 3, 4, and 5 are then concerned with the application and characterisation of continuous wave QCLs. In these chapters a widely tunable commercially produced EC-QCL is utilised as well as two DFB QCLs, one of which is used in tandem with a home-made mount and temperature controller. In Chapter 3 a number of sensitive detection techniques are compared with the employment of wavelength modulation spectroscopy, long path cells and optical cavities, and the narrow bandwidth of QCLs utilised to determine a previously unknown spectral constant of DBr. Chapters 4 and 5 then utilise the high power of an external cavity quantum cascade laser in sub-Doppler Lamb-dip and polarisation spectroscopy measurements and then a pump-probe experiment. The laser linewidth is investigated on a millisecond timescale returning a current noise limited value of c.a. 2 MHz and the fundamental linewidth of the device investigated by altering the injection current. Chapter 5 is concerned with the pump-probe experiment, directly measuring the hot band absorption in a ladder like transition (R(6.5)$_\frac{1}{2}$ $v=1\leftarrow0$ and P(7.5)$_\frac{1}{2}$ $v=1\leftarrow0$). The Bennett peak in the hot band is observed with a DFB-QCL swept at $\sim 0.15$ MHz ns$^{-1}$ and is seen not just as a pump bandwidth limited lineshape, but as a highly velocity selected rapid passage signal. The effect of pressure, pump and probe scan rate and power upon this rapid passage signal is also studied. It is further noted that rapid thermalisation occurs within $v=1$ such that at pressures above c.a. 30 mTorr a broad NO doublet absorption is observed beneath the Bennett peak from which a total population transfer of c.a. $16 \%$ can be estimated. Finally an experiment is discussed in which this population transfer could be increased for use in secondary applications. Chapter 6 then presents initial measurements with two prototype pulsed 3.3 \si{\micro\metre} QCLs considering the prospects of such devices. A Fabry-P\'{e}rot device is first studied using a Fourier transform spectrometer and temperature tuning used to produce a spectrum of the Q-branch of CH$_4$ around 3025 cm$^{-1}$. Experiments are then performed using a DFB QCL investigating the chirp rate of the system as an indicator of the rate of heat accumulation within the system. Heat management is of particular consideration when the sea-change is made from pulsed to continuous devices. For this device absorption spectra of two CH$_4$ transitions at 2971 cm$^{-1}$ are used to determine the chirp rate, which is found to be c.a. 1.8 GHz ns$^{-1}$, at least an order of magnitude higher than that of the longer wavelength pulsed devices considered in Chapter 2.

This thesis discusses the preliminary development of a microfluidic system for low concentration vapour analysis incorporating a novel analyte preconcentration method to extend vapour detection limits. The topicality of this subject is evidenced by the urgent requirement to detect vapours released by explosives or their manufacturing byproducts, allied to recent reports of gas phase detection of pathogen-related chemical markers. Commercially available, non-microfluidic, sensitive, delayed response, broadly specific, gasphase analysis methods have been developed recently. However microfluidic analysis offers the prospect of both the improved specificity of liquid phase analytical methods and increased sensitivity with fast response times. The necessary conditions to achieve a viable microfluidic vapour analysis system are discussed from collection, sampling, assay and measurement perspectives. Efficient, rapid, vapour collection into a liquid phase is predicated by large surface area to volume ratio phase-interfaces, as occur within microfluidic devices. Accordingly, research has focussed on stable, segmented gas and liquid microflows. The literature has concentrated on fixed structures and precise flow rate control to produce such segmented flow. In contrast, we have investigated pressure driven flow and small active valves in combination with precision patterned passive valves to provide deterministic control over flow and thus define gas and liquid segment sizes. This has allowed introduction of larger, precise gas volumes and hence gas/liquid ratios while still maintaining more stable flow patterns than those previously reported in the literature. Ethanol was employed as a completely soluble, volatile, ‘model’ analyte to assess collection efficiency. Research into detection focussed on a number of optical methods utilising either ‘wet’ or enzymatic chemistries. The Phase-to-Phase Extraction via a Chemical Reaction to give Lower Limits of Chemical Detection hypothesis (for the purpose of brevity this is shortened to ‘Chemical Amplification’ within this dissertation) was proposed. Thorough testing of the hypothesis using an enzyme catalysed reaction scheme has demonstrated its validity, and potential value if applied to ‘real world’ systems, particularly those for detecting low solubility analytes such as the explosive 2,4,6-trinitrotoluene (TNT) or its byproduct 2,4- dinitrotoluene (2,4-DNT).

The UK is reliant on landfill as a waste management option with some 72% w/w of municipal waste landfilled in 2003/04. This thesis advances an argument that landfill, as practised historically and currently, is unsustainable. This thesis demonstrates, specifically, that current legislative aftercare provisions of 30-60 years are inadequate with reference to modelled landfill completion times (the achievement of equilibrium status) of up to 2,000 years. Uniquely, the research quantifies the scale and significance of methane emissions during the early stages (up to 28 months waste age) of landfill operations at 21 UK landfills using a modified flux box. The onset of methanogenesis is quantified for the first time, using a series of in situ monitoring probes installed at one UK landfill site. A significant and novel finding is that the advective flow of landfill gas is preferentially dominated by lateral movement, evidenced here by examination of a predominantly municipal solid waste (MSW) landfill site in Southern England. The direct implications of this finding for the design of landfill gas management systems are discussed. For future landfills, this research has examined a number of UK scenarios in which the gas and leachate characteristics from waste residues going to landfill are modelled to the point of completion or achievement of equilibrium status. This analysis now allows for a comparative assessment of the future performance of landfills. Under these scenarios, completion times can be reduced in some instances {e.g. landfilling of compost and mechanical biological treatment residues) and extended in others (incinerator bottom ash). Problematic contaminants remain; notably arsenic, chromium and lead. Using the research herein, the work describes the application of a landfill gas management hierarchy. In part response to the requirements of the EU Landfill Directive, this provides a science-based framework for operators to maximise protection of the environment and human health from gaseous emissions. The research provides evidence that can be used by landfill managers seeking to maximise landfill collection efficiency. This contributes to regulators managing public and environmental health and is increasingly significant for climate change.