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This study aims to determine the concentration of 16 Polycyclic Aromatic Hydrocarbons (PAHs) in urban soils from West Yorkshire in order to determine what the factors are controlling their distribution and abundances. Although PAHs have been reported before from soils and sediments, the majority of these studies have come from China, sometimes with contrasting results, which emphasises the need to obtain equivalent data from other areas. Therefore this work provides the first measurements of their type from the area studied. Soil samples were collected from one hundred sites across an area from Bradford to Leeds on two occasions, one in autumn and one in the following summer. The soil samples were analyzed by X-ray diffraction and all found to have similar mineralogical composition, which was mainly silica and calcite. Trials using iodine as a marker for PAHs showed there were notable interactions between the minerals and PAHs, with calcium carbonate absorbing PAHs much more than silica. There is a negative correlation between the soil organic content (determined by loss on ignition) and PAHs, which confirms the PAH-mineral interaction. Gas chromatography with mass spectrometry (GC-MS) using targeted selected ion monitoring was used to determine and quantify PAHs in the one hundred soil samples with the aid of PAH external standards. The results showed highest concentrations of total PAHs in the same sample from Leeds from the autumn (1,525 ng/g) and in the summer (1,768 ng/g). In Bradford there was only moderate pollution of PAHs, the maximum being 122 ng/g. However the majority of data from Bradford showed lower levels of pollution in both summer and autumn. On the basis of prior published information, the ratio of these compounds has been used to help in identifying sources. In the samples collected from Bradford in both seasons and Leeds in autumn the PAH pollution originated from pyrogenic, biomass and petroleum combustion, however in the summer the source appeared more to be from a petrogenic source. These ratios in the samples which were collected from the area between Bradford and Leeds implied pyrogenic, biomass source of pollution in the autumn, but in the summer another source of organic compounds was indicated namely petroleum combustion. When the locations were resampled nine months later, after taking into account within-site variability, there was a strong indication that the PAH concentrations were higher. This might have been due to a seasonal effect, but when a further (third) subsample was taken at a later date it showed a further increase in PAH level which suggests the effect is accumulative rather than seasonal. The results were analysed using Principal Component Analysis (PCA) to determine whether the type of road had an effect on the concentration of the 16 PAHs compounds, but it was concluded that there was no such effect. However, the distance from the soil sample to the nearest road did have an effect on the concentration of the 16 PAH compounds, especially in soil samples having the shortest distance to the road. Traffic volume was also tested and found to influence the PAH concentrations. It is notable that, comparing the groupings from autumn with those from summer by cluster analyses, they largely had the same compounds grouping together in both cases; only two compounds differed at all in where they occurred in the clusters, with consistent patterns of grouping found for the other compounds. These analyses indicate that PAH compounds behave in a consistent way amongst groups of PAH compounds. The grouping of PAHs appears linked to their sources rather than number of rings or molecular weight.

This thesis addresses the question as to why multilevel politics is becoming an integral part of politics in Europe. Multilevel politics is conceptualized as a system which functions through a complex web of political relations within and across levels of decision making. The thesis argues that the rise of multilevel politics can be explained by its institutionalization in terms of the emergence, the evolution and especially the effects of relevant institutions. Based on a mixed-method research project, the influence of European institutions on subnational actors and the alignment of actor motives with institutional characteristics are empirically shown. The first chapter of the dissertation establishes the centrality of institutions for political transformation, examines the role of transnational and domestic institutions for multilevel politics, and contextualizes the research question in terms of institution-actor relations. The second chapter develops a new-institutionalist theoretical framework that explains the emergence, the evolution and the effects of the institutions, and formulates a series of hypotheses with regard to freestanding institutional influence, power distribution, material benefits and political identification. The third chapter outlines the mixed-method research design which addresses individual-level and institutional-level variations through a Europe-wide survey and a comparative case study. The fourth chapter on survey results shows generally favourable views on multilevel politics, and strong associations of these views with the independent variables under scrutiny. The fifth chapter specifies a multivariate model which includes all posited variables and confirms the majority of the hypotheses. Therefore, the new-institutionalist argument is broadly confirmed, while there is relatively weak evidence to sustain sociological explanations. The final chapter compares the Committee of the Regions and the Congress of Local and Regional Authorities, and examines the institutional characteristics which correspond to the hypothesized variables. It is then concluded that the two institutions share several overarching similarities, and display complementarity in other aspects.

This thesis presents the results of compositional and statistical analyses of Iron Age ironworking residues from sites in Scotland, England, Wales and France. As no framework for ferrous archaeometallurgy previously existed in the main research area of Scotland, a catalog of sites was compiled to determine where targeted scientific analyses could be of most use in creating a regional metallurgical profile. Fieldwork carried out at the site of Meunet Planches in France provided the non- British research component, as extant analyses matching this study’s temporal criteria were not available. A total of 80 new SEM-EDS samples were generated (58 from Scotland and 22 from France), and used together with existing site- and regional-level compositional studies to explore chemical behavior following the procedures laid out by Charlton (2007) and others. These included a range of multivariate statistical techniques such as Hierarchical Clustering Analysis (HCA), Principal Component Analysis (PCA), and Discriminant Analysis (DA). These approaches were considered within the wider discussion of smelting “systems” as defined by Dillmann and L’Heritier (2007), in an effort to visualize the relationship between compositional groups and parent geographic regions. Results indicate overall chemical homogeneity within and between the study regions, suggesting that the systems producing the slag were broadly similar in terms of their operation and reduction “efficiency”. This trend remains stable even when accounting for resource-based influence; implying that appreciable similarities existed between system operations (and therefore potentially human decisions) regardless of the size, age, or complexity of manufacturing industries. Deviation from this main compositional group, exhibited by only a handful of sites, seems to be similarly unrelated to temporal or geographic factors. Rather, it appears to follow the diffusion of slag between the two slag Optima identified by Rehren et al (2007), and on several of the outlier sites relates to the production of hypereutectoid steel.

Fermentation processes play an integral role in the manufacture of pharmaceutical products. The Quality by Design initiative, combined with Process Analytical Technologies, aims to facilitate the consistent production of high quality products in the most efficient and economical way. The ability to estimate and control product quality from these processes is essential in achieving this aim. Large historical datasets are commonplace in the pharmaceutical industry and multivariate methods based on PCA and PLS have been successfully used in a wide range of applications to extract useful information from such datasets. This thesis has focused on the development and application of novel multivariate methods to the estimation and control of product quality from a number of processes. The document is divided into four main categories. Firstly, the related literature and inherent mathematical techniques are summarised. Following this, the three main technical areas of work are presented. The first of these relates to the development of a novel method for estimating the quality of products from a proprietary process using PCA. The ability to estimate product quality is useful for identifying production steps that are potentially problematic and also increases process efficiency by ensuring that any defective products are detected before they undergo any further processing. The proposed method is simple and robust and has been applied to two separate case studies, the results of which demonstrate the efficacy of the technique. The second area of work concentrates on the development of a novel method of identifying the operational phases of batch fermentation processes and is based on PCA and associated statistics. Knowledge of the operational phases of a process can be beneficial from a monitoring and control perspective and allows a process to be divided into phases that can be approximated by a linear model. The devised methodology is applied to two separate fermentation processes and results show the capability of the proposed method. The third area of work focuses on undertaking a performance evaluation of two multivariate algorithms, PLS and EPLS, in controlling the end-point product yield of fermentation processes. Control of end-point product quality is of crucial importance in many manufacturing industries, such as the pharmaceutical industry. Developing a controller based on historical and identification process data is attractive due to the simplicity of modelling and the increasing availability of process data. The methodology is applied to two case studies and performance evaluated. From both a prediction and control perspective, it is seen that EPLS outperforms PLS, which is important if modelling data is limited.

Travelling wave ion mobility spectrometry (TWIMS) in combination with ultra-high performance liquid chromatography (UHPLC) and mass spectrometry (MS) has been applied successfully for the untargeted, global metabolic profiling of biofluids such as mouse plasma and saliva. Methods based on UHPLC-MS alone and in combination with ion mobility spectrometry (UHPLC-IM-MS) have been developed and validated for the untargeted metabolite profiling of saliva, obtained non-invasively by passive drool. Three separate metabolic profiling studies have been carried out in conjunction with bioinformatics strategies to identify potential metabolomic biomarker ions that are associated with efficacy of rice bran in colorectal cancer, physiological stress and that have the potential for the diagnosis of asthma. The advantages offered by the utility of ion mobility in UHPLC-MS based metabolic profiling studies, including the increased analytical space, mass spectral clean-up of contaminants such as PEG post-UHPLC-IM-MS analysis, enhancement of the selectivity of targeted metabolites as well as the potential for the identification of metabolites by comparison of ion mobility drift times have been highlighted. Ten potential metabolic biomarker ions of asthma have been identified from the moderate asthmatics from untargeted metabolite profiling of saliva by UHPLC-MS. A predictive model based on partial least squares discriminant analysis (PLS-DA) has been constructed using these ten discriminant ions, which demonstrates good predictive capability for moderate asthmatics and controls. Potential metabolic biomarker ions of physiological stress have been identified through untargeted metabolite profiling analysis of saliva samples collected before and after exercise by UHPLC-IM-MS. Valerolactam has been identified as a potential biomarker of physiological stress from saliva by comparison of retention time, ion mobility drift time and MS/MS spectra with a standard of δ-valerolactam.

The quest for a complete understanding of mixtures is a challenge which has stimulated the development of several techniques. One of the most powerful NMR-based techniques is known as Diffusion-Ordered SpectroscopY (DOSY), in which it is possible to distinguish the NMR spectra of chemical species with different hydrodynamic radii, i.e. with different self-diffusion coefficients. It allows the study of intact mixtures, providing information on the interactions within the mixture and saving time and money compared to other techniques. Unfortunately, DOSY is not very effective when signals overlap and/or the diffusion coefficients are very similar. This drawback has led to the development of new methods to overcome this problem. The present investigation is focused on developing some of these. Most DOSY datasets show multiplet phase distortions caused by J-modulation. These distortions not only hinder the interpretation of spectra, but also increase the overlap between signals. The addition of a 45º purging pulse immediately before the onset of acquisition is proposed as a way to remove the unwanted distortions. Most DOSY experiments use 1H detection, because of the higher sensitivity which is generally achieved. However, acquiring spectra with other nuclei such as 13C can reduce overlap problems. Two new sequences have been developed to maximize the sensitivity of heteronuclear DOSY experiments. In order to increase resolving power, it is also possible to incorporate another variable into diffusion experiments as a further dimension. If this results in an approximately trilinear dataset (each dimension varying independently), it is possible to extract physically meaningful information for each component using multivariate statistical methods. This is explored for the cases where the new variable is either the relaxation behaviour or the concentration variation (which can be measured during a reaction or in a set of samples with different concentrations for each component). PARAllel FACtor (PARAFAC) analysis can obtain the spectra, diffusional decay and relaxation evolution or kinetics for each of the components. In a completely different approach, the separation power of liquid chromatography has been combined in a novel way with the NMR potential for elucidating structures. NMR has been used previously as a precise way to measure average flow velocities, even in porous media. Using this capability to detect the different average velocities of solutes that occur in chromatographic columns ought to provide a new way of analysing mixtures with the same potential as LC-NMR, but faster and more simple. In such a flow system, a chromatographic column is introduced into the NMR probe and a 2D dataset is acquired and Fourier transformed to obtain the velocity distribution for each of the detected NMR signals.

A series of recent excavations on the 2nd Century AD Antonine frontier forts of the Midland Scottish valley, have produced results which suggest that the army was making its own pottery on an appreciable scale. This was at a time when pottery production was thought to have moved almost exclusively into civilian hands. The possible local ware groups identified by the excavations were largely independent of firm source indicators such as kiln and waster material and the number of available samples was often-small. A program of Neutron Activation and Thin Section petrological analyses was undertaken along with an investigation into Textural Analysis, a facet of the Petrological toolkit. The aim was both to define the site ware groups and a group of specialist vessels thought to be local to Scotland, the Mortaria, and to make statements as to their provenance. Although the Mortaria analysis was limited by problems of sample group size and availability, by improving the objectivity of the statistical handling of the derived data sets and developing methods for the high level study of textural data, the site ware groups were defined successfully at both the "intrall and "inter" site levels. The analyses also furnished interpretations as to the mode and nature of the site production schemes. Through the full analysis of' site Daub samples linked to more traditional provenancing techniques, in all but one case the ware groups could be assigned to the source sites, where contrasting production modes could be identified with military as opposed to civilian production.