Low valence cation doping of bulk Cr2O3: Charge compensation and oxygen vacancy formation

The different oxidation states of chromium allow its bulk oxide form to be reducible, facilitating the oxygen vacancy formation process, which is a key property in applications such as catalysis. Similar to other useful oxides such as TiO2, and CeO2, the effect of substitutional metal dopants in bulk Cr2O3 and its effect on the electronic structure and oxygen vacancy formation are of interest, particularly in enhancing the latter. In this paper, density functional theory (DFT) calculations with a Hubbard + U correction (DFT+U) applied to the Cr 3d and O 2p states, are carried out on pure and metal-doped bulk Cr2O3 to examine the effect of doping on the electronic and geometric structure. The role of dopants in enhancing the reducibility of Cr2O3 is examined to promote oxygen vacancy formation. The dopants are Mg, Cu, Ni, and Zn, which have a formal +2 oxidation state in their bulk oxides. Given this difference in host and, dopant oxidation states, we show that to predict the correct ground state two metal dopants charge compensated with an oxygen vacancy are required. The second oxygen atom removed is termed "the active" oxygen vacancy and it is the energy required to remove this atom that is related to the reduction process. In all cases, we find that substitutional doping improves the oxygen vacancy formation of bulk Cr2O3 by lowering the energy cost.

The ecology of the European hedgehog (Erinaceus europaeus) in rural Ireland

This study on the ecology of Irish hedgehogs (Erinaceus europaeus) has provided information on detection techniques, home range, habitat selection, hedgehog prey, nesting, courtship, genetics, road mortality, parasites, ageing and morphology of this species. Data were obtained from a focal study area in rural Cork, in which 24 radio tagged hedgehogs were monitored from June 2008 to June 2010. Further data were obtained through road kill surveys and the collection of hedgehog carcasses from around Ireland. Hedgehogs of both sexes were found to display philopatry. Habitat was not used in proportion to its availability, but certain habitats were selected and a similar pattern of habitat selection was evident in successive years. Hedgehogs preferred arable land in September and October and, unlike studies elsewhere, were observed to forage in the centre of fields. Badgers were regularly seen at the study site and did not appear to negatively affect hedgehogs’ use of the area. Instead the intra- and inter-habitat distribution of hedgehogs was closely correlated with that of their potential prey. Male hedgehogs had a mean annual home range of 56 ha and females 16.5 ha, although monthly home ranges were much more conservative. Male home range peaked during the breeding season (April-July) and a peak in road deaths was observed during these months. The majority of road kill (54%) were individuals of one year old or less, however, individuals were found up to eight and nine years of age. Genetic analysis showed a distinct lack of genetic variation amongst Irish hedgehogs and suggests colonisation by a small number of individuals. The ectoparasites, Archaeopsylla erinacei, Ixodes hexagonus and Ixodes canisuga were recorded in addition to the endoparasites Crenosoma striatum and Capillaria erinacei. In light of the reported decline in many areas of the hedgehogs’ range, it is a species of conservation concern, and this is the first study examining the ecology of the hedgehog in Ireland.

The senior female international managerial career move: a qualitative study in a European context

Research investigating the position of women in management has, largely, been confined within national boundaries. Over the last fifteen years, empirical studies of women in international management have been undertaken, predominantly in North America. In this research field, many questions remain unanswered or have been only partially addressed. The particular focus of this study is on the senior female international managerial career move in Europe — a relatively unexplored area. Fifty senior female expatriate managers were interviewed, representing a wide range of industry and service sectors. The study, for the first time, assesses an exclusively senior sample of female managers who have made at least one international career move. This study of senior females in international management makes a theoretical contribution, not only to the analysis of gender and international human resource management, but also to wider debates within the contemporary women in management and career theory literatures. The aims of the study were to develop an understanding of the senior female international career move in a European context in order to more fully understand both the covert and overt barriers that may limit women’s international career opportunities. The results of the study show that the senior international career move has largely been developed along a linear male model of career progression, a development which, taken together with gender disparity both in organisations and family responsibilities, frequently prevents women employees from reaching senior managerial positions. The study proposes a model of the senior female international managerial career move, thereby contributing primarily to the international human resource management literature. The implications of the study for research literatures in women in management and career theory are also explored and a future research agenda developed.

Tropospheric aerosol detection over Southern Ireland using a backscatter Raman lidar

Lidar is an optical remote sensing instrument that can measure atmospheric parameters. A Raman lidar instrument (UCLID) was established at University College Cork to contribute to the European lidar network, EARLINET. System performance tests were carried out to ensure strict data quality assurance for submission to the EARLINET database. Procedures include: overlap correction, telecover test, Rayleigh test and zero bin test. Raman backscatter coefficients, extinction coefficients and lidar ratio were measured from April 2010 to May 2011 and February 2012 to June 2012. Statistical analysis of the profiles over these periods provided new information about the typical atmospheric scenarios over Southern Ireland in terms of aerosol load in the lower troposphere, the planetary boundary layer (PBL) height, aerosol optical density (AOD) at 532 nm and lidar ratio values. The arithmetic average of the PBL height was found to be 608 ± 138 m with a median of 615 m, while average AOD at 532 nm for clean marine air masses was 0.119 ± 0.023 and for polluted air masses was 0.170 ± 0.036. The lidar ratio showed a seasonal dependence with lower values found in winter and autumn (20 ± 5 sr) and higher during spring and winter (30 ± 12 sr). Detection of volcanic particles from the eruption of the volcano Eyjafjallajökull in Iceland was measured between 21 April and 7 May 2010. The backscatter coefficient of the ash layer varied between 2.5 Mm-1sr-1 and 3.5 Mm-1sr-1, and estimation of the AOD at 532 nm was found to be between 0.090 and 0.215. Several aerosol loads due to Saharan dust particles were detected in Spring 2011 and 2012. Lidar ratio of the dust layers were determine to be between 45 and 77 sr and AOD at 532 nm during the dust events range between 0.84 to 0.494.

Studies relating to the population dynamics of the European badger (Meles meles) in Ireland

European badgers (Meles meles) are an important part of the Irish ecosystem; they are a component of Ireland’s native fauna and are afforded protection by national and international laws. The species is also a reservoir host for bovine tuberculosis (bTB) and implicated in the epidemiology of bTB in cattle. Due to this latter point, badgers have been culled in the Republic of Ireland (ROI) in areas where persistent cattle bTB outbreaks exist. The population dynamics of badgers are therefore of great pure and applied interest. The studies within this thesis used large datasets and a number of analytical approaches to uncover essential elements of badger populations in the ROI. Furthermore, a review and meta-analysis of all available data on Irish badgers was completed to give a framework from which key knowledge gaps and future directions could be identified (Chapter 1). One main finding suggested that badger densities are significantly reduced in areas of repeated culling, as revealed through declining trends in signs of activity (Chapter 2) and capture numbers (Chapter 2 and Chapter 3). Despite this, the trappability of badgers was shown to be lower than previously thought. This indicates that management programmes would require repeated long-term efforts to be effective (Chapter 4). Mark-recapture modelling of a population (sample area: 755km2) suggested that mean badger density was typical of continental European populations, but substantially lower than British populations (Chapter 4). Badger movement patterns indicated that most of the population exhibited site fidelity. Long-distance movements were also recorded, the longest of which (20.1km) was the greatest displacement of an Irish badger currently known (Chapter 5). The studies presented in this thesis allows for the development of more robust models of the badger population at national scales (see Future Directions). Through the use of large-scale datasets future models will facilitate informed sustainable planning for disease control.

Pretty good governance: balancing policy drivers and stakeholder interests in developing fisheries ecosystem plans

The central research question that this thesis addresses is whether there is a significant gap between fishery stakeholder values and the principles and policy goals implicit in an Ecosystem Approach to Fisheries Management (EAFM). The implications of such a gap for fisheries governance are explored. Furthermore an assessment is made of what may be practically achievable in the implementation of an EAFM in fisheries in general and in a case study fishery in particular. The research was mainly focused on a particular case study, the Celtic Sea Herring fishery and its management committee, the Celtic Sea Herring Management Advisory Committee (CSHMAC). The Celtic Sea Herring fishery exhibits many aspects of an EAFM and the fish stock has successfully recovered to healthy levels in the past 5 years. However there are increasing levels of governance related conflict within the fishery which threaten the future sustainability of the stock. Previous research on EAFM governance has tended to focus either on higher levels of EAFM governance or on individual behaviour but very little research has attempted to link the two spheres or explore the relationship between them. Two main themes within this study aimed to address this gap. The first was what role governance could play in facilitating EAFM implementation. The second theme concerned the degree of convergence between high-level EAFM goals and stakeholder values. The first method applied was governance benchmarking to analyse systemic risks to EAFM implementation. This found that there are no real EU or national level policies which provide stakeholders or managers with clear targets for EAFM implementation. The second method applied was the use of cognitive mapping to explore stakeholders understandings of the main ecological, economic and institutional driving forces in the Celtic Sea Herring fishery. The main finding from this was that a long-term outlook can and has been incentivised through a combination of policy drivers and participatory management. However the fundamental principle of EAFM, accounting for ecosystem linkages rather than target stocks was not reflected in stakeholders cognitive maps. This was confirmed in a prioritisation of stakeholders management priorities using Analytic Hierarchy Process which found that the overriding concern is for protection of target stock status but that wider ecosystem health was not a priority for most management participants. The conclusion reached is that moving to sustainable fisheries may be a more complex process than envisioned in much of the literature and may consist of two phases. The first phase is a transition to a long-term but still target stock focused approach. This achievable transition is mainly a strategic change, which can be incentivised by policies and supported by stakeholders. In the Celtic Sea Herring fishery, and an increasing number of global and European fisheries, such transitions have contributed to successful stock recoveries. The second phase however, implementation of an ecosystem approach, may present a greater challenge in terms of governability, as this research highlights some fundamental conflicts between stakeholder perceptions and values and those inherent in an EAFM. This phase may involve the setting aside of fish for non-valued ecosystem elements and will require either a pronounced mind-set and value change or some strong top-down policy incentives in order to succeed. Fisheries governance frameworks will need to carefully explore the most effective balance between such endogenous and exogenous solutions. This finding of low prioritisation of wider ecosystem elements has implications for rights based management within an ecosystem approach, regardless of whether those rights are individual or collective.

The analytical approach of the European Court of Human Rights in surveillance cases—the implications, justifications, and future of the Court’s reasoning, with a focus on the legislative impact in Ireland

A notable feature of the surveillance case law of the European Court of Human Rights has been the tendency of the Court to focus on the “in accordance with the law” aspect of the Article 8 ECHR inquiry. This focus has been the subject of some criticism, but the impact of this approach on the manner in which domestic surveillance legislation has been formulated in the Party States has received little scholarly attention. This thesis addresses that gap in the literature through its consideration of the Interception of Postal Packets and Telecommunications Messages (Regulation) Act, 1993 and the Criminal Justice (Surveillance) Act, 2009. While both Acts provide several of the safeguards endorsed by the European Court of Human Rights, this thesis finds that they suffer from a number of crucial weaknesses that undermine the protection of privacy. This thesis demonstrates how the focus of the European Court of Human Rights on the “in accordance with the law” test has resulted in some positive legislative change. Notwithstanding this fact, it is maintained that the legality approach has gained prominence at the expense of a full consideration of the “necessary in a democratic society” inquiry. This has resulted in superficial legislative responses at the domestic level, including from the Irish government. Notably, through the examination of a number of more recent cases, this project discerns a significant alteration in the interpretive approach adopted by the European Court of Human Rights regarding the application of the necessity test. The implications of this development are considered and the outlook for Irish surveillance legislation is assessed.

Assessment of dietary background exposure of the Irish adult population to dioxins and PCBs particularly taking into account additional exposure due to the 2008 Irish dioxin food contamination incident

Irish monitoring data on PCDD/Fs, DL-PCBs and Marker PCBs were collated and combined with Irish Adult Food Consumption Data, to estimate dietary background exposure of Irish adults to dioxins and PCBs. Furthermore, all available information on the 2008 Irish pork dioxin food contamination incident was collated and analysed with a view to evaluate any potential impact the incident may have had on general dioxin and PCB background exposure levels estimated for the adult population in Ireland. The average upperbound daily intake of Irish adults to dioxins Total WHO TEQ (2005) (PCDD/Fs & DLPCBs) from environmental background contamination, was estimated at 0.3 pg/kg bw/d and at the 95th percentile at 1 pg/kg bw/d. The average upperbound daily intake of Irish adults to the sum of 6 Marker PCBs from environmental background contamination ubiquitous in the environment was estimated at 1.6 ng/kg bw/d and at the 95th percentile at 6.8 ng/kg bw/d. Dietary background exposure estimates for both dioxins and PCBs indicate that the Irish adult population has exposures below the European average, a finding which is also supported by the levels detected in breast milk of Irish mothers. Exposure levels are below health based guidance values and/or Body Burdens associated with the TWI (for dioxins) or associated with a NOAEL (for PCBs). Given the current toxicological knowledge, based on biomarker data and estimated dietary exposure, general background exposure of the Irish adult population to dioxins and PCBs is of no human health concern. In 2008, a porcine fat sample taken as part of the national residues monitoring programme led to the detection of a major feed contamination incidence in the Republic of Ireland. The source of the contamination was traced back to the use of contaminated oil in a direct-drying feed operation system. Congener profiles in animal fat and feed samples showed a high level of consistency and pinpointed the likely source of fuel contamination to be a highly chlorinated commercial PCB mixture. To estimate additional exposure to dioxins and PCBs due to the contamination of pig and cattle herds, collection and a systematic review of all data associated with the contamination incident was conducted. A model was devised that took into account the proportion of contaminated product reaching the final consumer during the 90 day contamination incident window. For a 90 day period, the total additional exposure to Total TEQ (PCDD/F &DL-PCB) WHO (2005) amounted to 407 pg/kg bw/90d at the 95th percentile and 1911 pg/kg bw/90d at the 99th percentile. Exposure estimates derived for both dioxins and PCBs showed that the Body Burden of the general population remained largely unaffected by the contamination incident and approximately 10 % of the adult population in Ireland was exposed to elevated levels of dioxins and PCBs. Whilst people in this 10 % cohort experienced quite a significant additional load to the existing body burden, the estimated exposure values do not indicate approximation of body burdens associated with adverse health effects, based on current knowledge. The exposure period was also limited in time to approximately 3 months, following the FSAI recall of contaminated meat immediately on detection of the contamination. A follow up breast milk study on Irish first time mothers conducted in 2009/2010 did not show any increase in concentrations compared to the study conducted in 2002. The latter supports the conclusion that the majority of the Irish adult population was not affected by the contamination incident.

Aspects of the biology of the parasite Bonamia ostreae with a view to gaining a greater understanding of how to alleviate its impact on the European flat oyster, Ostrea edulis.

The parasite Bonamia ostreae has decimated Ostrea edulis stocks throughout Europe. The complete life cycle and means of transmission of the parasite remains unknown. The methods used to diagnose B. ostreae were examined to determine sensitivity and reproducibility. Two methods, with fixed protocols, should be used for the accurate detection of infection within a sample. A 13-month study of two stocks of O. edulis with varying periods of exposure to B. ostreae, was undertaken to determine if varying lengths of exposure would translate into observations of differing susceptibility. Oyster stocks can maintain themselves over extended periods of time in B. ostreae endemic areas. To identify a well performing spat stock, which could be used to repopulate beds within the region, hatchery bred spat from three stocks found in the North sea were placed on a B. ostreae infected bed and screened for growth, mortality and prevalence of infection. Local environmental factors may influence oyster performance, with local stocks better adapted to these conditions. Sediment and macroinvertebrate species were screened to investigate mechanisms by which B. ostreae may be maintaining itself on oyster beds. Mytilus edulis was positive, indicating that B. ostreae may use incidental carriers as a method of maintaining itself. The ability of oyster larvae to pick up infection from the surrounding environment was investigated by collecting larvae from brooding oysters from different areas. Larvae may acquire the pathogen from the water column during the process of filter feeding by the brooding adult, even when the parents themselves are uninfected. A study was undertaken to elucidate the activity of the parasite during the initial stage of infection, when it cannot be detected within the host. A naïve stock screened negative for infection throughout the trial, using heart imprints and PCR yet B. ostreae was detected by in-situ hybridisation.

The emerging strategic partnership between the European Union and the African Union

Many among the emerging generation of political elites in Africa see the role the European Union (EU) plays in the maintenance of an unprecedented period of peace in Western Europe as an inspirational example of the manner in which the African Union (AU) can contribute to peace and stability in Africa. This doctoral thesis examines security cooperation between the EU and the AU, with a particular focus on the nature and substance of that cooperation. It suggests that despite the establishment of various EU–AU institutions and ties with a role in security policy and cooperation, such security cooperation is limited in substance. This study argues that EU–AU security cooperation is especially constrained by the emergence of alternative partners, most notably China, and by failures of implementation and follow-through. Two case studies, the first dealing with EU–AU cooperation in peacekeeping, and the second addressing the silent water crisis along with the link between water and security, have been analysed in detail to determine the effectiveness and sustainability of the EU–AU partnership. A number of important lessons for regionalism, interregionalism and multilateralism are drawn from the bond between the EU and the AU. This doctoral thesis will prove that, despite an emphasis on the problematic term ‘strategic’ by both EU and AU policymakers, EU–AU cooperation is limited and somewhat lacking in strategic direction. The cooperation between the EU and the AU focuses mainly on EU financial support for AU peacekeeping and specific projects in Africa (e.g. in the water sector), as well as on a limited political dialogue. Nonetheless, the EU–AU link represents the most comprehensive partnership the AU has with any non-African actor. This study will furthermore demonstrate that the United Nations (UN) is an indispensable third-party to their relationship and it is therefore more appropriate to speak of the AU–EU–UN nexus. This doctoral thesis concludes that the AU–EU–UN nexus is an important example of interregionalism in a global context and that such interregionalism is an important emerging part of global governance.

A craniometric study of population dynamics and social organisation in the European upper Palaeolithic and Mesolithic

The purpose of this study is to explore aspects of social organisation during the Upper Palaeolithic and Mesolithic periods using craniometric data. Different hypotheses were tested using geometric morphometrics, alongside traditional craniometric data. The clustering of individuals from the same site, as well as a correspondence to an isolation-by-distance model—particular in the Mesolithic samples—points to population structure within these groups. Moreover, discontinuities in cranial traits between the early Upper Palaeolithic and later periods could suggest that the Last Glacial Maximum had a disruptive effect on populations in Europe. Differences in social organisation can often result from cultural norms regarding post-marital residence. Such differences can be tested by comparing cranial data to that of geographic information. Greater variation in male cranial traits relative to females, after controlling for location, suggests that the overall pattern of residence during the Upper Palaeolithic and Mesolithic was one of matrilocality. It has been suggested that coastal occupation was density dependent and these populations show a greater degree of sedentism than their inland counterparts. Moreover, it has been proposed that coastal areas were not continuously occupied until the Late Pleistocene due to spatial restrictions that would adversely affect reproductive opportunities. This study corroborates the pattern seen in cranial traits corresponded with that of a more sedentary population. The results are consistent with the hypothesis that coastal populations are more sedentary than inland populations during these periods. This study adds new information regarding the social dynamics of prehistoric populations in Europe and sheds light on some of the conditions that may have paved the way for the transition to agriculture

Voltage properties of optically injected long wavelength VCSELs: Theory and experiment

Future high speed communications networks will transmit data predominantly over optical fibres. As consumer and enterprise computing will remain the domain of electronics, the electro-optical conversion will get pushed further downstream towards the end user. Consequently, efficient tools are needed for this conversion and due to many potential advantages, including low cost and high output powers, long wavelength Vertical Cavity Surface Emitting Lasers (VCSELs) are a viable option. Drawbacks, such as broader linewidths than competing options, can be mitigated through the use of additional techniques such as Optical Injection Locking (OIL) which can require significant expertise and expensive equipment. This thesis addresses these issues by removing some of the experimental barriers to achieving performance increases via remote OIL. Firstly, numerical simulations of the phase and the photon and carrier numbers of an OIL semiconductor laser allowed the classification of the stable locking phase limits into three distinct groups. The frequency detuning of constant phase values (ø) was considered, in particular ø = 0 where the modulation response parameters were shown to be independent of the linewidth enhancement factor, α. A new method to estimate α and the coupling rate in a single experiment was formulated. Secondly, a novel technique to remotely determine the locked state of a VCSEL based on voltage variations of 2mV−30mV during detuned injection has been developed which can identify oscillatory and locked states. 2D & 3D maps of voltage, optical and electrical spectra illustrate corresponding behaviours. Finally, the use of directly modulated VCSELs as light sources for passive optical networks was investigated by successful transmission of data at 10 Gbit/s over 40km of single mode fibre (SMF) using cost effective electronic dispersion compensation to mitigate errors due to wavelength chirp. A widely tuneable MEMS-VCSEL was established as a good candidate for an externally modulated colourless source after a record error free transmission at 10 Gbit/s over 50km of SMF across a 30nm single mode tuning range. The ability to remotely set the emission wavelength using the novel methods developed in this thesis was demonstrated.

Exploring alternatives for milk quality improvement and more efficient dairy production in a smallholder farming context – case study: Mantaro Valley (Peru)

Consumer demand is revolutionizing the way products are being produced, distributed and marketed. In relation to the dairy sector in developing countries, aspects of milk quality are receiving more attention from both society and the government. However, milk quality management needs to be better addressed in dairy production systems to guarantee the access of stakeholders, mainly small-holders, into dairy markets. The present study is focused on an analysis of the interaction of the upstream part of the dairy supply chain (farmers and dairies) in the Mantaro Valley (Peruvian central Andes), in order to understand possible constraints both stakeholders face implementing milk quality controls and practices; and evaluate “ex-ante” how different strategies suggested to improve milk quality could affect farmers and processors’ profits. The analysis is based on three complementary field studies conducted between 2012 and 2013. Our work has shown that the presence of a dual supply chain combining both formal and informal markets has a direct impact on dairy production at the technical and organizational levels, affecting small formal dairy processors’ possibilities to implement contracts, including agreements on milk quality standards. The analysis of milk quality management from farms to dairy plants highlighted the poor hygiene in the study area, even when average values of milk composition were usually high. Some husbandry practices evaluated at farm level demonstrated cost effectiveness and a big impact on hygienic quality; however, regular application of these practices was limited, since small-scale farmers do not receive a bonus for producing hygienic milk. On the basis of these two results, we co-designed with formal small-scale dairy processors a simulation tool to show prospective scenarios, in which they could select their best product portfolio but also design milk payment systems to reward farmers’ with high milk quality performances. This type of approach allowed dairy processors to realize the importance of including milk quality management in their collection and manufacturing processes, especially in a context of high competition for milk supply. We concluded that the improvement of milk quality in a smallholder farming context requires a more coordinated effort among stakeholders. Successful implementation of strategies will depend on the willingness of small-scale dairy processors to reward farmers producing high milk quality; but also on the support from the State to provide incentives to the stakeholders in the formal sector.

Locating the transnational: representations and aesthetics of the city in contemporary European cinemas

This thesis focuses on two Western European cinematic cities, and two unique periods of their respective nations’ histories, in a bid to “locate” the transnational within a contemporary European milieu. I argue that my geo-cinematic case studies are emblematic of broader questions of the problematics of national identity in contemporary Europe in the face of cross-national flows yet, as a result of their representations as cities both “anchored” and “in flux”, they reject a European postnational identity. Through its engagement with cinematic Rome as the “Eternal City” of Europe and cinematic Dublin as the “newly Europeanised” city, my thesis traces how representations and aesthetics of the urban spaces of these two cities correspond with the tensions at the heart of the respective eras in question. Via the figures that inhabit it, navigate it and search for it, the city is utilised to highlight fixity and mobility, centrality and dislocation, in explicit and implicit ways, amid the rapidly changing landscape of its national terrain. It is through my analyses of the filmed places and sociopolitical, socioeconomic and sociocultural spaces of these capital cities under the rubric of the transnational that this research demonstrates the “pluralities” of the construct in its cinematic manifestations. It is also my aim to evaluate the concept of cinematic transnationalism when identifying and accounting for representations of a specific national, historical timeframe, when the momentousness of the changes that occur is not bound by the national, but rather is reflective of the influence of both domestic and external forces. To this end, my thesis draws attention to instances in which the nation is shown to persist and resist dilution, arguing that it is only against the backdrop and continuity of the nation (in its evershifting guises) that the transnational can be conceived in representative and aesthetic terms.