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Roads are an inevitable result of human expansion across the globe, but result in unintended consequences for the other species we share our planet with, both directly (e.g. through deaths due to wildlife-vehicle collisions), as well as indirectly (e.g. through habitat degradation, and providing a barrier to animal movement). These effects are so wide-reaching that a new term – road ecology – was coined in 1998 to describe the study of these ecological impacts. The overall aim of this thesis is to increase our knowledge of road ecology and begins by reviewing the literature on the scientific value of monitoring wildlife roadkill (Chapter 2). Five continuous years of data from a citizen science roadkill recording scheme ‘Project Splatter’ is then used to examine temporal trends in wildlife roadkill in the UK (Chapter 3). Camera-trapping experiments were utilised to gain additional insight into the behavioural effects of roads on wildlife, namely the behaviour of scavengers of roadkill (Chapter 4), as well as the effects of light and sound pollution caused by roads on the behaviour of wildlife (Chapter 5). A review of the existing literature in Chapter 2 demonstrates how studying roadkill has enhanced our knowledge in several critical areas of ecological study, I also show how even with limited geographical and taxonomic estimates, in excess of 400 million vertebrates are killed on roads worldwide each year. Chapter 3 shows that the temporal patterns of roadkill in the UK are peculiar to a given species, but are remarkably consistent between years, and poses the hypothesis that the observed temporal patterns are driven by species-specific seasonal changes in behaviour. In Chapter 4, I show how scavengers of roadkill can remove carcasses very quickly, potentially leading to an under-estimation of true roadkill numbers - 76% of experimentally placed carcasses were removed within 12 hours, and the number of scavenging events peaked in the first few hours of daylight. Finally, Chapter 5 demonstrates how road traffic noise is likely to negatively influence wildlife behaviour by causing animals to avoid particularly noisy areas, as well as by altering xiii their behaviour to increase the amount of vigilance behaviour, leading to a reduction in time available to spend foraging. The research presented within this thesis has expanded the current knowledge of road ecology, particularly within a UK context, and has continued to demonstrate how data collected by members of the public (through citizen science projects) can have important scientific value. This deeper understanding of the impacts of roads on wildlife is important if we wish to reduce the ecological impacts of our ever-expanding road system.

The following research marks the beginning of the new field of research on theatmospheric transport of microplastic and its potential terrestrial and oceanicsource. Taking atmospheric deposition samples from the French Pyrenees Iwas able to illustrate the first atmospheric transport of microplastics of at least95km using hysplit4 back trajectory modelling. Further to this I used highvolume sampling technique to show first evidence of free-troposphericmicroplastic at an altitude of 2877masl at the Pic du Midi observatory in France. I also showed the ocean to be a source of atmospheric microplastics bysampling the sea breeze in varying wind events showing first evidence of oceanto atmosphere transfer.

In the subject area of conservation and ecology, human disturbance is classified as any anthropogenic activity that elicits a response in an animal that would otherwise not occur under non-human related conditions. When this change in behaviour negatively impacts an animal’s energy budget it has the potential to reduce reproductive output and survival, and so ultimately, human disturbance may affect animal populations. Therefore, understanding mechanisms that lead to human disturbance and its energetic cost are vital in understanding if human disturbance may affect animal populations in the present and the future. To investigate these topics, this study looked at different aspects of human disturbance relative to two species of wildfowl, Brent goose (Branta bernicla, L.) and wigeon (Mareca penelope, L.), on the Exe Estuary, during the winters of 2017-2018 and 2018-2019. This included: identifying environmental variables that lead to overlaps in space and time between wildfowl and humans, assessing the disturbance cost within those overlaps, differentiating costs of disturbance relative to human disturbance types, understanding the compensation ability of wildfowl to deal with human disturbance, and identifying the thresholds of human disturbance wildfowl are capable of experiencing without negative impacts. Primary findings indicated that conditions associated with overlaps between wildfowl and humans were predominantly associated with food availability for wildfowl and site accessibility conditions for humans. Within these overlaps, wildfowl were found to be disturbed for a minority of the time, with Brent goose being disturbed approximately 6% of the time, and wigeon being disturbed approximately 5% of the time. Costs associated with these disturbances were found to increase if wildfowl were feeding when disturbed compared to resting. Additionally, overlaps and disturbances from different human activity types were found to vary, indicating that some human activity types may be more threatening, in terms of disturbance than others. An investigation of the literature identified that animals use their ‘spare-rest’ time to compensate for the time and energy costs associated with human disturbance. This finding, along with a calculation of energetic costs relative to energetic needs of wildfowl on the Exe Estuary, identified that time and energy costs due to human disturbance, at the time of this study, were well below any thresholds for compensation. Projections of human disturbance using an individual-based model (IBM) validated that Brent goose would need to be disturbed at least 7 times per hour and wigeon would need to be disturbed at minimum of 12 times per hour before they would be unable to compensate. These results indicate that Brent goose and wigeon populations on the Exe Estuary are currently under no immediate threat from human disturbance. Furthermore, this study has identified more widely applicable variables that lead to human disturbance in general, and mechanisms for determining if and when it is causing a problem for wildlife populations. Understanding and predicting these types of impacts will then help preserve animal populations and biodiversity richness throughout a wide variety of ecosystems.

Urbanisation is one of the greatest threats to biodiversity, causing significant habitat loss and species declines. However, with appropriate management, urban green spaces such as road verges can support biodiversity and provide ecosystem services. To improve the provision of these benefits, suitable management needs to be identified. The first objective was to investigate the impact of reducing mowing frequency of urban road verges on botanical and invertebrate communities through a controlled experimental trial. The second objective assessed residents' perceptions of the trial on their road, along with a range of hypothetical road verge management scenarios. The final objective was to provide baseline information on how different urban road verges are managed across England and assess which factors influence decisions. A reduction in mowing frequency over one season significantly increased vegetation height, Araneae and total invertebrate abundance. It did not alter botanical species richness, flowering abundance, forb abundance and the number of invertebrate orders, when compared to the established mowing regime. However, residents experiencing these changes significantly preferred road verges mown at the established, higher frequency, both when compared to the actual reduced mowing and to other hypothetical scenarios, despite recognising that current management may not be best for biodiversity. With increasing budgetary constraints, road verge managers are considering or implementing alternative management such as reducing mowing frequency. Factors influencing management decisions include finance and resources, public perception and actions, safety, spatial context, biodiversity and environmental benefits, physical factors and departmental and councillor input. These results indicate that urban road verge management involves a complex set of tradeoffs, where win-win scenarios may not always be possible. It also highlights where more considered management could increase the benefits from what is a ubiquitous, but often overlooked habitat, potentially playing an important role in cultivating greater connection to nature within the urban setting.

In this study a number of analytical techniques for the screening, quantification and identification of brominated flame retardants in consumers’ products, electric and electronic waste and indoor dust is explored. The presented work can be conceptually divided in two parts: - The first explores, evaluates and pushes the limits of solid sampling techniques (i.e. X-Ray Fluorescence and Laser Ablation Inductively Coupled Plasma Mass Spectrometry) as a tool for the total elemental quantification of Bromine and its use as a metric for BFR content in consumers’ goods and waste. The XRF method proved to be accurate to 94% (relative to LA-ICP-MS results), making the technique (used with the developed calibration) reliable for the quantification of Br in polymers. REEs concentrations obtained with LA-ICP-MS were used to evaluate the origin of contaminants in FCAs and toys. - The second part explores the suitability of solid sampling techniques (that do not require sample preparation) and simplified liquid sampling techniques (that require sample preparation in the form of solvent assisted extraction) for the compound specific, semi quantitative evaluation of BFRs in plastic material and indoor dust. DIP-HRMS and DART-HRAM showed sufficient linearity over the calibration range and mass determination accurate enough to unequivocally identify BDE209 in polymeric matrices. GC-ICP-MS analysis performed with ad-hoc developed hardware provided reliable data for the semi-quantitative evaluation of indoor dust PBDE profile.

Isoprene (2-methyl 1, 3-butadiene) is the most abundant non-methane BVOC (biogenic volatile organic compound) released into the atmosphere. Terrestrial plants are the primary producers of isoprene and release 500-750 million tonnes of isoprene per year, to protect themselves from abiotic environmental stresses such as heat and reactive oxygen species. Many studies have explored isoprene production but very little is known about consumption of isoprene by microbes. Cleveland and Yavitt in 1998 (Cleveland and Yavitt 1998), and more recently Khawand et al. 2016 (Khawand et al. 2016), demonstrated that microbes isolated from terrestrial environments are capable of using isoprene as sole carbon and energy source. By applying cultivation-dependent and cultivation-independent techniques, such as DNA Stable Isotope Probing (Dumont and Murrell 2005), my objective was to determine the distribution, diversity and activity of isoprene-degrading bacteria in the terrestrial environment. Isoprene-degrading microbes were enriched by adding 13 to 50 ppm isoprene to microcosms using topsoil from a willow tree and topsoil/leaves from an oil palm tree. DNA stable isotope probing, using 13C-labelled isoprene, assisted in revealing the diversity of active isoprene degraders by labelling organisms that incorporated the isoprene, directly or indirectly. PCR retrieval of partial 16S rRNA genes from this DNA revealed labelled members of the genera Ramlibacter, Variovorax, Rhodococcus and Methylibium, for willow soil, and Rhodococcus, Gordonia, Aquabacterium, Aquincola, Methylobacterium and members from the Sphingomonadaceae family, for the oil palm tree. Using cultivation-dependent methods I isolated seven phylogenetically different isoprene-utilizing bacteria of the genera Rhodococcus, Nocardioides and Variovorax from willow soil environment; another four phylogenetically different bacteria belonging to the genera Gordonia, Sphingopyxis and Sphingobacterium from the oil palm tree. Results suggest Rhodococcus is a cosmopolitan isoprene-degrader, present in a variety of environments, and different isoprene-degrading bacteria were found associated to willow and oil palm trees.

Tree stems can act as a conduit for trace greenhouse gases (GHG) produced in the soil. However, the majority of studies describing tree stem fluxes of methane (CH₄) and nitrous oxide (N₂O) have focused on wetland ecosystems. Tree stem fluxes of GHGs on free-draining soils are understudied, but they are assumed to be a source of CH₄ and a weak source of N₂O. The work presented in this thesis aimed to determine how climatic variables, soil abiotic conditions, and tree species influence CH₄ and N₂O fluxes in forests on free-draining soil. Soil and stem CH₄ and N₂O fluxes were measured in lowland tropical rainforest in Panama, Central America and temperate woodland in the UK, using chambers installed on the forest floor or strapped to individual stems of two common tree species. Air samples were collected every two to four weeks during 5 months in 2014 and during November 2015 at the tropical site, and between February 2015 and January 2016 at the temperate site. Tree stem CH₄ fluxes differed significantly between species at both sites and stem N₂O fluxes also differed between species at the tropical site. However, there was little variation in soil CH₄ or N₂O fluxes. At both sites, tree-mediated CH₄ fluxes declined from positive values (emission) at the stem base to negative values (uptake) higher up. Stem CH₄ fluxes generally increased significantly with solar radiation, suggesting a link to photosynthetic activity mediated by tree water transport. Collectively, these results show that trees on free-draining soils could act as net sinks for CH₄ and N₂O. These findings will improve GHG budgets because tree stem uptake is currently unaccounted for. In particular, if uptake of CH₄ by tree stems on free-draining soils is widespread, the global terrestrial CH₄ sink could be much larger than currently estimated.

Flooding from intense rainfall, resulting from convection, causes millions of pounds of damage each year. However, convection has limited predictability, often resulting in short lead times for warnings of such events. This research aims to determine the spatial scales of perturbation growth in convective-scale forecasts for different environmental conditions over the British Isles. The convective adjustment timescale identifies whether cases are in equilibrium with the large-scale forcing, so can be used to quantitatively classify convection into the regimes of quasi-equilibrium and non-equilibrium. A method is found to calculate the timescale based on criteria considering its variability and the environment in which it is calculated. The most appropriate method uses a Gaussian kernel to spatially smooth convective available potential energy and precipitation accumulation fields before the calculation. A model climatology is created over the summers of 2012-2014 (due to limited operational data from the United Kingdom Variable resolution, UKV, configuration of the Met Office United Model) to understand the characteristics of the regimes over the British Isles. In summer 85% of convection is in convective quasi-equilibrium, with more nonequilibrium events in the south and west of the British Isles. The UKV is perturbed with Gaussian buoyancy perturbations to create an ensemble. These perturbations represent unresolved processes within the boundary layer. The perturbation growth is examined across a spectrum of cases and it is shown that events at the non-equilibrium end of the spectrum have higher spatial predictability than those at the equilibrium end (O(1 km) vs. O(10 km)), implying more localised growth in nonequilibrium, than quasi-equilibrium, environments. This research has implications in the interpretation of forecasts for defining regions when issuing weather warnings associated with convection. The research also has implications for adaptive forecasting, in which high-resolution forecasts are used for nonequilibrium convection and large-member ensembles are used for events in convective quasi-equilibrium.

Contemporary climate change politics, dominated by neoliberal and ecological modernisation framings, has reached an impasse. This thesis investigates whether a Marxist critique focused on trade unions might offer an alternative approach. It critically analyses the social science literature on climate change and utilises insights from the employment relations literature to interrogate trade union activities. The thesis makes original contributions to both the climate change and employment relations literatures. First, it offers a critique of the dominant climate politics and suggests an alternative framing. Second, it proposes a theorisation of organised workers and trade unions as strategic climate actors, applying Hyman's triangular model of market, society and class to understand union behaviour on climate change. Third, it contains a theoretically informed and empirically grounded investigation of UK trade union policy and practice on climate change at the start of the 21 st century. The main findings are that some socialists, trade unionists and activists in the UK have introduced a working class perspective into climate discourse, including challenges to property relations, climate inequality and through mobilisation. Some trade unionists have foreground the occupational aspects of climate change and climate policy, and made distinctive demands for a radical just transition, climate jobs and socially useful work. Trade union climate representatives ("green reps") in some workplaces have made an independent contribution to climate mitigation and adaptation. The occupation of the Vestas wind turbine manufacturing factory and the resulting climate solidarity illustrate the potential power of workers' climate action. The principal conclusions are that workers have the interest and collective capacity to reduce greenhouse gas emissions, to address the differential impacts of climate and climate policy, and to coalesce other actors to tackle climate change. The recent experience of UK trade unions suggests they have a vital role to play as climate actors and, suitably reconfigured, the capability to lead a renewed climate movement.

Brominated flame retardants (BFRs) are ubiquitous in indoor air and dust, leading to human exposure and resultant concerns about adverse impact on health. Despite elevated concentrations in dust, little is known about how BFRs transfer to dust from treated products. A test chamber was constructed to investigate pathways via which the polybrominated diphenyl ethers (PBDEs) and hexabromocyclododecanes (HBCDs) migrate from source materials to indoor dust. These were: (1) BFRs volatilise and subsequently partition to dust, (2) particles or fibres of the source abrade, transfering to dust directly (3) direct source-dust contact results in transfer. A HBCD treated textile curtain, and a PBDE TV casing were both tested. Partitioning post volatilisation was a less effective mechanism than abrasion. Direct source-dust contact resulted in effective and rapid transfer. A forensic microscopy investigation on ‘real world’ dust of elevated BFR content identified polymer particles containing BDE-209, likely originating from a BFR treated polymeric material indicating abrasion. An \(in\) \(vitro\) extraction test investigated the bioaccessibility of dust contaminated \(via\) pathways (1) and (2). Results indicate bioaccessibility may be less efficient from samples containing elevated concentrations of BFRs, and from dusts contaminated primarily via abrasion. More detailed research is essential to confirm these findings.

If the response to climate change is to include a transition to a low carbon economy, then the role of small businesses will be vital. As employers, innovators, polluters and carbon users, small businesses have significant combined impacts and opportunities. Within the framework of ecological modernisation, government policy has taken a largely voluntary approach to engaging small businesses with pro-environmental behaviour. Research has consistently found small businesses to be resistant to business greening and taken a predominantly positivist approach to identifying the barriers and drivers to behaviour and to measuring the effectiveness of different policy measures. In this study, the Schwartz Value System (SVS) is used within a qualitative research design to contribute new insight into how managers make sense of climate change. The thesis demonstrates the role of values in sensemaking and the need to engage with individuals within small businesses through the value-based frames they hold. In particular, this research shows that the win-win approach aimed at encouraging SMEs to save money, save the planet through voluntary engagement strategies over-simplifies managerial motivation. The managers in this study drawing on the self-enhancing value of Power most clearly reflected win-win ideas, except that they encapsulated the save money but not the save the planet message. Environmental protection, found within Universalism values, was only demonstrated by managers drawing on Achievement. In making sense of climate change, managers constructed their ideas using a mix of self enhancing, self-transcending, open and conservation values. To fully engage SME managers with climate change, policy makers need to take a more sophisticated approach to explicitly engaging individual with values.

Global temperatures are predicted to rise by 2-2.5°C by 2065, profoundly affecting the Earth's environment. The response of ecosystems to past climate fluctuations can inform on how systems will respond in the future. This thesis focuses on Quaternary environmental changes in West Africa, a region important because of its high ecological value and role in the global carbon cycle. In 2004, the International Continental Drilling Program recovered c. 291 m of sediments spanning the last c. 1 Myr from Lake Bosumtwi (Ghana). Pollen, charcoal and nitrogen isotopes (ᵟ15N) were analysed from the most recent c. 150m (c. 520 kyr). The latitudinal position and long duration of this core makes it unique for understanding West African monsoon dynamics and vegetation change. To aid characterisation of the Bosumtwi pollen succession, an atlas of present-day pollen was constructed for 364 pollen and spore taxa. The pollen record from Bosumtwi reveals dynamic vegetation change over the last c. 520 kyr, characterized by eleven biome shifts between savannah and forest. Savannah vegetation is dominated by Poaceae (>55%) associated with Cyperaceae, Chenopodiaceae-Amaranthaceae and Caryophyllaceae. Forest vegetation is palynologically diverse, but broadly characterised by Moraceae, Celtis, Uapaca, Macaranga and Trema. Low ᵟ15N values correspond to forest expansion and these are driven by high lake levels. The timescale indicates that the six periods of forest expansion correspond to global interglacial periods. The record indicates that the wettest climate occurred during the Holocene, and the driest during Marine Isotope Stage 7. The vegetation and ᵟ15N records show a strong response to glacial-interglacial variability between 520- 320 kyr and 130- 0 kyr. Between 320- 130 kyr there is a weaker response to glacial-interglacial cycles probably related to high eccentricity during the peak of the 400-kyr component of eccentricity, with high eccentricity resulting in greater seasonality and ultimately drier conditions.

Global environmental change fundamentally affects plants and their interactions with other species, and this has profound impacts on communities and ultimately ecosystems. In order to understand the mechanisms involved, we need to elaborate on the combined effects of different global change drivers on multiple levels of plant organization, including the biochemical level (production of defence compounds), the whole organism, the population, and the plant-herbivore interaction level. This thesis investigates (1) the combined effects of factors related to climate change and habitat fragmentation on Brassica nigra and (2) the effects of Zn soil pollution on the heavy metal hyperaccumulator Noccaea caerulescens at these different levels. Common garden and greenhouse experiments with B. nigra applied drought stress and elevated CO2 to examine climate change impacts, while crossing treatments (inbreeding and between-population outbreeding) were used to investigate habitat fragmentation effects. Heterosis was lost under drought stress, and there were several interactive effects of the experimental treatments that varied within and among populations. In a greenhouse experiment with N. caerulescens, plants were grown on soil with different amounts of zinc. Plants had greater herbivore resistance when grown on Zn-amended soil, and invested more in herbivore tolerance when grown on soil without added Zn. In general, the results indicate that factors related to global environmental change have complex and interactive effects on different levels of plant organization. The findings are discussed in terms of their implications for ecology, evolution and conservation.

The destruction and fragmentation of natural habitat is the leading driver of the current extinction crisis. As a result, a research area has emerged focused on studying ecology in islands of natural habitat surrounded by a sea of anthropogenic land uses, so called ‘habitat islands’. However, this research has largely been undertaken on small-medium scales, generally in single systems. Furthermore, many habitat island studies have used previous results and theory derived in the context of oceanic island research. Thus, this thesis aims to examine a variety of macroecological and biogeographical patterns using a large number of purely habitat datasets sourced from both the literature and my own sampling, with the objective of teasing out any general statistical patterns. The various macroecological and biogeographical patterns can be grouped under four broad headings: 1) species–area relationships (SAR), 2) nestedness, 3) species abundance distributions (SADs), and 4) species incidence functions (function of area). Overall, it was found that there were few hard macroecological generalities that hold in all cases across habitat island systems. This is because most habitat island systems are highly disturbed environments, with a variety of confounding variables and undesirable species (e.g. species associated with human land uses) acting to modulate the patterns of interest. Nonetheless, some clear patterns did emerge. In particular, it was found that the power model was by the far the best general SAR model for habitat islands. The slope of the island species–area relationship (ISAR) was related to the matrix type surrounding archipelagos, such that habitat island ISARs were shallower than true island ISARs. Significant compositional and functional nestedness was rare in habitat island datasets, although island area was seemingly responsible for what nestedness was observed. Species abundance distribution models were found to provide useful information for conservation in fragmented landscape, but the presence of undesirable species substantially affected the shape of the SAD. Species incidence function curves were found to vary across space for a given species, but not in any systematic manner. In conclusion, this thesis finds that the application of standard island biogeography theory to habitat islands is too simplistic. It is hoped that the results of this thesis will act as a catalyst for a more macroecological approach to habitat island research, and a starting point for the development of an integrated theory of habitat islands.

carbon dioxide (C02) emission to atmosphere (due to fossil fuel fired energy consumption) is a major contributor to greenhouse effect which is causing climate change. Integrated Gasification Combined Cycle (IGCe) power plants have greater adaptability to C02 capture in comparison to the state of the art technology (for Greenhouse gas mitigation). Economic infeasibility, Techno-Economic uncertainty and lack of operational experience are some of the major hurdle preventing further penetration of this technology. As a result, larger amount of contingency is applied to the project cost (for various equipment and sUb-systems of the plant). The aim of this research is to develop a significantly detailed process model (of Hydrogen sulphide and Carbon Dioxide capture from syngas) and to develop a realistic estimate of the size of the plant (to conduct the economic assessment). Detailed process design is developed for H2S and C02 capture from syngas using physical solvent. The physical solvent chosen for this research is a blend of various di-methyl ether of poly ethylene glycol (DMEPEG). Rate based simulations are conducted (using Pro-Treat software) to determine the equipment size, the operating condition and the process performance parameters. Various unit operations (within the process) have been optimized using sensitivity study of various process parameters. Several energy saving features have been introduced in the process which finally result in Reboiler Duty (for H2S capture) as low as 30.67 GJ/Ton (which is 99.5 % of feed) and Energy consumption (for C02 capture) as low as 52.422 kW-Hr/Ton (which is 88 % of feed). Suppliers have been identified for various process equipment and their suggestions have been incorporated to develop the process model, to evaluate the process performance and to estimate the cost of the plant.

Long term, continuous and high frequency measurements of CHBr3 and CH2Br2 from five different AGAGE stations have been presented and analysed in this thesis. The CHBr3 and CH 2Br2 mixing ratio ranged from 0.93 ppt to 65.26 ppt. Their background concentration is approximately 0.98 and 1.01 ppt for the Northern Hemisphere. CHBr3 and CH 2Br2 data correlated very well with each other across all five stations. At coastal locations, both bromocarbons displayed a seasonal variation induced by local, summer production. The seasonal variation detected at Jungfraujoch station was dictated by the stronger summer loss processes. Higher CHBr3 and CH2Br2 concentrations often come from coastal sectors, suggesting macroalgae sources. Through AGAGE measurements, the global CHBr3 emission is estimated to be between 1 ± 0.04 Tg Br y(l and 4.9 ± 0.2 Tg Br y(l (based on 57 to 280 Gg Br yr-1 emission of CH2Br2) via a calculated 0.085 ([CH2Br21/[CHBr31) source ratio estimate. CHBr3, CH2Br2 and several halocarbons' degradation schemes and their subsequent halogen chemistry scheme has been incorporated into a three-dimensional tropospheric Lagrangian Chemistry Transport model - STOCHEM CRI v2-R5 . STOCHEM-CRI allowed us to validate the high emission estimate derived from AGAGE measurements, predict the distribution of the source and product gases and study the impact of CHBr3/Bromine on tropospheric species such as ozone. CHBr3 and CH2Br2 estimated lifetimes in STOCHEM-CRI are shorter than the literature values. Their organic product gases are all short lived species that rapidly degrade and produce inorganic bromine product gases. CHBr3 and CH2Br2 zonal plots indicate possible source gas injection of Br into the stratosphere. Zonal plots of Brx (mainly as Br, BrO, HOBr and BrN02) suggest the possibility of product gas injection of Br into the stratosphere. CHBr3 and halogen chemistry has reduced the overall oxidation capacity of the lower troposphere. 1.12% of the total 0 3 burden is lost per Tg of Br emitted into the model. Other radical species' burden also decreased, while hydrocarbon burdens increased

Anthropogenic C02 release is leading to a wide range of oceanic environmental changes that may influence the survivability of marine organisms in the future. Environmental change varies regionally, and Southern Ocean calcifying organisms are considered to be particularly at risk from change, due to low pre-existing pH conditions and rapidly increasing temperatures. UVic model data from the Southern Ocean is used to assess environmental change in the region, and shows the importance of considering the variability as well as the magnitude of change. Since pre-industrialisation, the four Southern Ocean locations analysed showed a modern pH range entirely outside the historic range. The southern west Antarctic Peninsula region is considered the most vulnerable due to historic environmental stability, increased variability in the modern, and the widest gap between historic and modern carbonate chemistry variability envelops. The geochemistry and crystal structure of eight species of Antarctic bivalves were investigated, and four of these species were used to assess organism response to environmental change since pre-industrialisation from the western Antarctic Peninsula to South Georgia. Bivalve response varied between and within species: Lissarca miliaris showed a decrease in shell robustness over time; Lissarca notorcadensis showed one instance of no change and another of increased robustness; and Limatula pygmaealLimatula ovalis showed no change. There was no correlation between sites identified as vulnerable in the UVic model, and bivalve response. Mytilus californianus, a temperate bivalve species, from Tatoosh Island on the NW Pacific coastline of the USA, were similarly tested as pH has declined in the region four times faster than the global average. Bivalve shells showed a change in biomineralisation, resulting in increased robustness from the historic to the modern. The variability in response illustrates that some species have sufficient plasticity to be unaffected by environmental change, some may struggle to survive in future oceans and others have the capacity to adapt on short timescales.

In this thesis the effects of individual and multiple environmental stressors (physical and chemical) are examined in inbred and outbred zebrafish (Danio rerio, Hamilton), a model species used in ecotoxicology and environmental risk assessment (ERA). The central question addressed is, are inbred laboratory animals representative and protective of wild populations? That is, are inbred fish equally or more sensitive to chemicals and other stressors compared with more outbred (wild) fish? A combination of tools and approaches incorporating traditional (eco)toxicology and population genetics have been employed, together with more contemporary molecular genetics and population modelling, to compare and contrast a range of responses in inbred and outbred zebrafish exposed to the endocrine disrupting chemical clotrimazole and/or temperature elevation in the laboratory. The choice of test species was based on our broad understanding of its basic biology, extending from the molecular level to the population level, and its wide use as a model organism in (eco)toxicology. Selection of the test chemical clotrimazole and temperature was based on a shared mode of action, aromatase inhibition, and therefore their ability to block oestrogen production, impair reproduction, promote male development and skew population sex ratios in zebrafish. A cascade of responses were compared in inbred and outbred zebrafish, including changes in the levels of expression of genes for gonadal aromatase and other steroidogenic enzymes, circulating sex steroid hormones, gonadal sex differentiation and development (via gonadal histopathology) and reproductive fitness (female fecundity, paternity and viability of embryos). Amongst the most striking results were directional skews in sex ratio towards males in response to clotrimazole (Chapter 5) and elevated temperature exposure (Chapter 7). Inbred fish were generally more responsive compared to outbreds, which showed evidence of physiological and developmental compensation, resulting in lower male-sex skews and superior fitness in terms of male reproductive success (paternity and viability of embryos). The greater effects observed in inbred fish were attributed to inbreeding×environment interactions and the amplification of inbreeding depression. Although no empirical genetic evidence of this mechanism is presented (loss of heterozygosity at quantitative trait loci and concomitant loss of heterosis and/or the expression of recessive, deleterious alleles in homozygotes), supporting evidence was provided by increased phenotypic variance in some apical endpoints in inbred fish, including specific growth rate and fecundity. This increased variance also has the potential to counteract the higher levels of response observed in inbreds, because the power to detect statistically significant changes in responses is reduced. This trade-off was demonstrated for specific growth rate. Crucially, significant male-sex ratio skews (>80%) were induced at substantially lower clotrimazole exposure concentrations (1.7 µg l-1) in combination with elevated temperature (33°C), compared with exposure concentrations (43.7 µg l-1) generating similar sex ratio skews at the standard test temperature of 28°C. These temperatures represent current and predicted 2100 (elevated) mean temperatures in the zebrafish’s native India and Bangladesh. Although the lowest observed effect concentration was an order of magnitude above the predicted environmental concentration for clotrimazole, it is conceivable that combined environmental exposures to similarly acting chemicals (e.g. other azole compounds used in crop protection, veterinary and human medicine) could produce similar effects to those we observed. The consequent effects of sex ratios skews and reduced fitness (fecundity and embryo viability) on per capita population growth rate (r) and extinction probability were predicted in inbred versus outbred zebrafish populations using stochastic population viability analysis. The results showed that the observed male-skews >80% threaten small zebrafish populations with fewer than 100 breeding adults (<20 adult females). However, small reductions of 2-3% in embryo-juvenile (age 0+) survivorship (including simulated inbreeding depression) were more influential on r and extinction probability than large sex ratio skews and/or reduced female fecundity. The results presented in this thesis support the contention that chemical effects may be exacerbated by other environmental stressors, but also illustrate the importance of considering biological (genetic), as well as physical and chemical interactions in cumulative ERA. Greater sensitivity of inbred versus outbred organisms to the effects of environmental stressors on sexual differentiation and reproductive fitness offers a margin of safety to ERA and the protection of wildlife populations (excluding those that are severely inbred and critically endangered). This is because, as originally stated, laboratory organisms used in ERA are generally more inbred than their wild counterparts. Nevertheless, more attention should be paid to the origin, breeding history and genetics of laboratory strains. This will help to ensure consistency between studies and testing laboratories and provide more confidence in extrapolating the results to wild populations.

As the nanotechnology industry grows rapidly, the release of nanoparticles (NPs) will increase in the environment. The special functional properties of NPs bring uncertainty on how they will affect exposed organisms. Aquatic organisms may be particularly at risk because this environmental compartment acts as a sink for most contaminants. Two major NPs used in the nano industry are silver (Ag) and titanium dioxide (TiO2). Ag is being exploited principally for its antimicrobial properties and TiO2 for its photocatalytic properties. There is evidence that both of these particles can induce harmful effects in exposed organisms but our understanding on the mechanisms for their effects, uptake and fate of these NPs is still very limited, especially for environmentally relevant exposure regimes. The studies conducted during this thesis investigated the potential for biological effects to Ag and TiO2 in the aquatic environment using the zebrafish (Danio rerio). Uptake and effects of a range of NPs of different sizes (Ag -10nm, 35nm and a bulk counterpart 600-1600nm, and TiO2 -7nm, 10nm, 35nm and a bulk counterpart 134nm) were assessed in zebrafish embryos exposed via the water column. It was established that TiO2NPs had no adverse effects on zebrafish embryos even at an exposure concentration of 25 000 µg/L. In contrast, AgNPs induced dose dependent lethality and the AgNP (35nm) was most toxic. At lower exposure concentrations Ag induced a number of morphological defects in embryos and apoptosis was seen to occur around 7 hours post fertilisation (hpf) in the extended yolk sac region of the embryo. Coating the AgNP materials with citrate and fulvic acid significantly reduced toxicity. Coherent Anti Raman Scattering (CARS) microscopy was applied to the exposed embryos and indicated that there was little, if any uptake of Ag/TiO2 NPs as particles into the embryo. CARS however showed very significant aggregation of both NPs at the chorion surface. It was concluded from this work that the toxicity observed was most likely mediated via silver ions dissociating from the AgNPs. In this work, the metallothionein (mt2) gene was activated (detected using whole mount in-situ hybridisation-WISH) at sublethal exposure concentrations (500 µg AgNP/L and 12 µg AgNO3/L) in the extended yolk sac region of the embryo (24hpf), which is known to be a site of metal detoxification. In a second series of studies to explore the mechanisms and target tissues for AgNPs, WISH was adopted in early life stages of zebrafish using various genes that were markers of stress responses. These genes were metallothionein (mt2), glutathionine S-Transferase Pi (gstp), glutathionine S-Transferase Mu 1 (gstm1), hemeoxygenase 1 (hmox1) and ferritin heavy chain 1 (fth1). In the first instance the ontogeny of expression of these genes was established for up to 12 days post fertilisation (dpf) to determine the optimal time point to test for responses of these genes for the particle exposures. Early life stages of the zebrafish were exposed to citrate coated AgNP (10nm, 500 µg/L), Ag bulk (160nm, 500 µg/L) and silver ions (20 µg/L). The Ag materials induced upregulation in mt2, gstp and gstm1 in various target tissues including the yolk sac, olfactory bulbs, lateral line neuromasts, ionocytes in the skin and in regions of the head. Silver ions affected the same target tissues and induced the same gene responses as AgNPs, albeit there were differences in the levels of these gene responses between these two treatments. In contrast, both hmox1 and fth1 were downregulated as a result of Ag exposure. To further explore the molecular mechanism by which AgNP toxicity occurs, an Nrf2 (a transcription pathway involved in oxidative stress) mutant zebrafish was included in exposures to Ag. These studies found that mt2 and gstp were both expressed at lower levels in the Nrf2 mutant zebrafish exposed to Ag materials compared with in the wild type zebrafish. This suggests that the Nrf2-Keap pathway plays a key role in controlling the expression of these genes that are responding to the AgNPs exposures. This work demonstrated that WISH provided a highly effective integrative approach for identifying target tissues exposure to the different silver materials and for exploring functional pathways of effects. In the final study of this thesis, adult breeding zebrafish were fed AgNP via the diet to investigate uptake and accumulation into target organs, the possibility of maternal transfer and the potential for subsequent effects in exposed offspring. Adult zebrafish were fed at a rate of 5µg Ag/g at 3% of their body weight to Ag materials (AgNP 10nm and AgB 600-1600nm) over a period of 26 days. No effects were seen in the adult fish on any of the measures taken of fitness (condition factor index, gonadsomatic index, hepatosomatic index, haematocrit index). Ag did not significantly affect fecundity (numbers of eggs spawned) or fertility (numbers of eggs fertilised). A detectable level of uptake of Ag in target organs occurred only in the AgNP treatments: liver (up to 2.1 µg/g in males) and gonads (up to 0.5 µg/g in males), suggesting particle size plays a role in the uptake and translocation through membranes into target organs and thus an enhanced bioavailability for AgNP compared with AgB. Maternal transfer was only detectable in the AgNP treatment (up to 0.43 ng Ag/per embryo). Gene responses of mt2 and gstp measured in the subsequent offspring via WISH analysis at 24 hpf indicated significant mt2 upregulation occurred after 2 weeks of adult exposure in both AgNP and AgB treatments. This demonstrates the potential for maternal exposure effects for exposure to AgNPs. Furthermore, challenging the subsequent embryos to the same Ag materials and measuring responses of mt2 via WISH indicated de-sensitisation to Ag in offspring where adults were treated with both nano and bulk forms of Ag. This finding has important considerations for risk assessments for silver base materials. Overall, the findings presented in this thesis have provided a body of evidence to show that silver material on a nanoscale may be of a greater hazard to fish and this warrants further investigation to consider more appropriately the potential risks associated with discharge of AgNPs into the aquatic environment.

This thesis examines the influence of environmental movement actors on press coverage about climate change between 1986 and 2008. It assesses the extent to which social dynamics that resemble Habermas' ideal of communicative action are important for frequent and significant impacts on media coverage. The thesis is based on four strands of research: interviews, Internet- and literature-sourced material to build a description of the British environmental movement; frequency counts of climate change coverage across four UK national newspapers; a frame analysis of a 1000+ article sample of this coverage; and background research into the political and media contexts of the climate change issue, involving further interviews and textual sources. High profile political interventions before 1992 cemented a pattern of media coverage that privileged government, science, and business over the environmental movement. Thus, although the amount of climate change coverage increased, the proportion of climate change-related coverage that referred to environmental movement groups did not keep pace. Instead, the most significant influence was political. The UK government's adoption of a target of 80% reductions in carbon emissions by 2050 followed a period of intense movement activity on climate change in which radical, reformist, and conservationist organisations were often well-networked, while reflecting different relationships with 'grass-roots' actors. Formal organisations, such as Greenpeace, Friends of the Earth and RSPB regularly and routinely made press releases, but these were associated with declines in news coverage more frequently than increases. The introduction of new relationships, actors, or pen;;pectives, such as the creation of Stop Climate Chaos and the Climate Camp, or senior politicians' support for legislation on climate, tended to be associated with the most significant positive impacts upon newspaper coverage. Interactions between environmental movement actors and the media decreased because interdependency between them declined as a wider r, II range of voices joined the debate about climate change, and as the Internet offered environmental groups alternative means to communicate. These findings support Habermas' notion of communicative action as a valuable avenue by which to pursue the study of influence.

This thesis explores how rally drivers in Scotland perceive environmental issues and the environments through which they drive. The overarching aim behind this is to think about a group of people who may be more hostile towards questions of environmental responsibility, and look at how such stakeholders reason round their behaviours and perceive environmental issues. I argue that due to the potentially farreaching impacts of contemporary environmental challenges, it is crucial to take seriously the viewpoints and values of those who are perhaps not so willing to engage with environmental issues. The work draws on several bodies of literature. First is work in environmental philosophy on the practical contribution of this sub-discipline, in particular environmental pragmatism. Second is thinking in sociology and human geography on responsibility, especially the interface between responsibility and care. Third is recent material in geography on the body and movement, in particular the burgeoning field of automobility. These issues are addressed through a three-fold research design. Ethnographic and participatory techniques are used to foster an understanding of what exactly ‘the environment’ might mean to rally drivers (and indeed other users of the forest with whom rallying may come into conflict) and how it is experienced. In-depth interviews and subsequent narrative analysis seek to delve further into participants’ narratives and life histories in order to get a handle on how rally driving sits in relation to broader life contexts. Finally, two small-scale participatory projects with rally organisers relating to environmentally-responsible practice look at how this all comes together when participants make practical responses to environmental challenges. The key conclusions arising from the empirical data are that environmental problems are experienced through a range of senses, with different groups using different sensory ‘evidence’ to make claims about environmental damage; that in some cases stakeholders’ views of environmental issues are based on perceived conflict with others as opposed to actual conflict; and that the values activities such as motor sport may represent are just as significant as their physical environmental impacts. In terms of the broader applicability of this research, I suggest two things. Firstly, that one of the key challenges in responding to contemporary environmental issues lies in thinking through how publics link up their everyday practices with much bigger discourses on global environmental change. Secondly, that careful and critical reflection on the rich narratives of place and people, and on the range of emotions shaped by embodied experience, can go some way to explaining why people may persist with more environmentally damaging practices in spite of ethical and environmental criticisms.

Fish can bioconcentrate complex mixtures of xenobiotics arising from exposure to wastewater effluents discharged into surface waters. Wastewaters contain a complex mixture of organic compounds and little is known about their uptake into fish and their health effects. In this study, a chemical profiling approach was used to characterize the profile of xenobiotics and their metabolites (the xenometabolome) in biofluids (bile and plasma) of juvenile rainbow trout (Oncorhynchus mykiss) exposed to a wastewater effluent. Metabolite profiles of effluent-exposed fish were compared with that from control fish exposed to uncontaminated river water. Samples were analysed by ultra performance liquid chromatography-time-of-flight mass spectrometry and data analysed by multivariate statistics. Exposure to effluent resulted in accumulation in trout bile of alkylsulfophenyl and alkylpolyethoxy carboxylates, as well as glucuronide conjugates of nonylphenol ethoxylates, alcohol ethoxylates, naphthols, chlorinated xylenols and phenoxyphenols, chlorophenes, resin acids, mefenamic acid and oxybenzone. Nonconjugated or sulphate conjugates of many of these contaminants were also detected in plasma of effluent-exposed trout. In addition, changes in the concentrations of endogenously derived metabolites were also detected in trout plasma, and these included an increase in blood bile acids, methylbutryolcarnitine and a decrease in sphingosine levels. These observations were verified in a further exposure of sexually mature roach (Rutilus rutilus) to concentrations of the same effluent. Exposure to 50% or 100% effluent resulted in dose dependent increases in blood concentrations of xenobiotics, taurocholic acid, syprinol sulphate and lysophospholipids and decreases in sphingosine levels. This work reveals the complex nature of xenobiotics accumulating in effluent-exposed fish together with the identification of changes in concentrations of lipid metabolites associated with hepatotoxicity. These results reveal, for the first time, that metabolite profiling techniques can be used to screen for uptake of complex mixtures of contaminants into fish and also for the detection of natural metabolite pathways in the organism that are disrupted due to exposure to multiple xenobiotics.

This thesis is intended to derive deterministic models, from different techniques and disciplines, to predict indoor air pollution originated from the outdoors where/when such measurement cannot be undertaken. It focuses on modelling indoor concentrations of particulate matter (PM) in naturally ventilated buildings taking into account spatial and temporal variations. The models developed have considered variables potentially influencing indoor PM concentrations, such as, outdoor PM concentrations, meteorological conditions, room characteristics/orientation, natural ventilation and human activity patterns. Analyses undertaken during this research have provided a number of findings concerning the ability to predict indoor PM concentrations as a function of ambient air pollution. In particular, results indicate how ambient PM concentrations and time-activity data can be used to help assess indoor PM levels.

This thesis firstly investigates the effect of the cestode parasite Schistocephalus solidus on the reproduction of its intermediate host, the three spined stickleback. The results indicated that the parasite reduced host reproduction and the physiological basis behind this was established. In males, parasite infection reduced the fish’s ability to produce 11-ketotestosterone which resulted in reduced reproductive behaviour and sexual development. In infected females, vitellogenin production was reduced which prevented egg maturation. The adaptive nature of these changes seemed to be variable among different populations. This variation may result from genetic differences in the host or parasite population, co-evolutionary processes or reflect differences in the environmental conditions experienced by populations. The second part of this thesis investigates the effect of two types of anthropogenic stressors – endocrine disrupting chemicals and temperature change as an outcome of global climate change – on disease progression in the stickleback-Schistocephalus system. The results indicated that the natural steroid 17β estradiol (E2) had a significant impact on disease progression in a sex and dose dependent manner, with males exposed to the high 100ngLˉ¹ E2 treatment harbouring significantly larger parasites compared to females in this treatment and fish from the lower E2 and solvent control treatment. Elevated temperatures were also found to significantly increase parasite growth and reduce host growth. In addition, a behavioural study showed that fish harbouring infective parasites seek out high temperatures which could be adaptive on the part of the parasite as it would allow them to grow faster and potentially increase their reproductive output. The clear outcome of this thesis is that anthropogenic stressors increase disease progression in the stickleback-Schistocephalus system and this is likely to lead to reduced host reproduction and increased parasite transmission and reproduction, potentially leading to the evolution of higher virulence in this host-parasite interaction.

Diurnal temperature range (DTR) declined over global land during 1950-2004. Climate model simulations have shown DTR is sensitive to many forcings including solar radiation, CO2, aerosols and land cover change. Relationships between DTR trends and potential forcings or feedbacks fall short of providing causal evidence due to paucity of observations and a focus on average changes over the diurnal cycle rather than changes within the diurnal cycle. Non-linear regression of seasonal and geographic variations in DTR found cloud cover, soil moisture, distance inland, solar radiation, elevation and vegetation type explained 80% of the variation in DTR. These factors are likely influential for regional DTR trends. Surface net longwave radiation was linearly related to seasonal variations in DTR and explained over 95% of the' variation in tropical regions. The NCAR SCCM model was used to simulate the response of DTR and surface energy fluxes to 2 x CO2 and -2% solar forcings. An ensemble of 24 model runs with forcing applied hourly through the diurnal cycle was replicated 20 times in 18 locations. Under CO2 forcing, the increase in DTR at the first '.···r time-step after forcing (0.01 DC) was offset by rapid adjustments and climate feedbacks during the three-day period after forcing. Rapid adjustments to surface sensible and latent heat fluxes totalled +1.55 Wm·2 driven by tropospheric adjustments to clouds and humidity. Under solar forcing, the reduction in DTR at the first time-step after forcing (-0 .l5DC) was subsequently magnified (-0 .l7DC) by feedbacks. Rapid adjustments were dominated by a reduction in surface sensible heat (-1.39 Wmo2) offset by an inversely correlated increase in surface latent heat (+0.98 Wmo2). There was no evidence of a tropospheric rapid adjustment with solar forcing. CO2 induced diurnal changes in downwelling longwave radiation and rapid adjustments in surface heat fluxes have likely contributed to the global DTR trend. 7 1 I

The health impact of short-term exposure to air pollution has been the focus of much recent research, the majority of which is based on time-series studies. A time-series study uses health, pollution and meteorological data from an extended urban area. Aggregate level data is used to describe the health of the population living with the region, this is typically a daily count of the number of mortality or morbidity events. Air pollution data is obtained from a number of fixed site monitors located throughout the study region. These monitors measure background pollution levels at a number of time intervals throughout the day and a daily average is typically calculated for each site. A number of pollutants are measured including, carbon monoxide (CO); nitrogen dioxide (NO2); particulate matter (PM2.5 and PM10), and; sulphur dioxide (SO2). These fixed site monitors also measure a number of meteorological covariates such as temperature, humidity and solar radiation. In this thesis I have presented extensions to the current methods which are used to estimate the association between air pollution exposure and the risks to human health. The comparisons of the efficacy of my approaches to those which are adopted by the majority of researchers, highlights some of the deficiencies of the standard approaches to modelling such data. The work presented here is centered around three specific themes, all of which focus on the air pollution component of the model. The first and second theme relate to what is used as a spatially representative measure of air pollution and allowing for uncertainty in what is an inherently unknown quantity, when estimating the associated health risks, respectively. For example the majority of air pollution and health studies only consider the health effects of a single pollutant rather than that of overall air quality. In addition to this, the single pollutant estimate is taken as the average concentration level across the network of monitors. This is unlikely to be the average concentration across the study region due to the likely non random placement of the monitoring network. To address these issues I proposed two methods for estimating a spatially representative measure of pollution. Both methods are based on hierarchical Bayesian methods, as this allows for the correct propagation of uncertainty, the first of which uses geostatistical methods and the second is a simple regression model which includes a time-varying coefficient for covariates which are fixed in space. I compared the two approaches in terms of their predictive accuracy using cross validation. The third theme considers the shape of the estimated concentration-response function between air pollution and health. Currently used modelling techniques make no constraints on such a function and can therefore produce unrealistic results, such as decreasing risks to health at high concentrations. I therefore proposed a model which imposes three constraints on the concentration-response function in order to produce a more sensible shaped curve and therefore eliminate such misinterpretations. The efficacy of this approach was assessed via a simulation study. All of the methods presented in this thesis are illustrated using data from the Greater London area.

Climate change is the most important issue of our time due to its potential to very seriously disrupt the life sustaining systems of planet Earth as well as its intersec-tions with other important challenges facing humanity. The United Nations Frame-work Convention on Climate Change is the key platform upon which the political process of international climate change politics takes place. The aim of this work is to produce an analysis of the role of transnational climate change advocacy networks in this political process and their internal power dynamics and thus contributing to the understanding of a crucial aspect of this political process. To advance this aim, this thesis engages with two objectives. First, a detailed ethnography is developed which serves to illustrate the political work of the environmental advocacy NGOs involved within this process, especially those that are members of Climate Action Network International (CAN-I). This approach is suitable to uncover the internal dynamics and structures of that NGO network as well as its complex and multi-layered relationships within the larger political configuration of the UNFCCC treaty process. Secondly, the investigation is advanced by analysing this ethnography through the lens of a critical theory of the public sphere. In particular, this analysis features more contemporary conceptualisations of the public sphere which stress the multiplicity of the public sphere concept including notions such as internal and external public spheres, counterpublics, and nested public spheres. Owing to this research design, the thesis has a degree of hybridity: it is expressly both an empirical thesis, with strong empirical flavour imparted by the focus on the detailed ethnographic account, as well a theoretical thesis offering an original contribution that is advanced throughout the thesis. The main theoretical thesis and contribution is that the theory of the public sphere is appropriate to analyse the political practice of civil society engagement on a transnational level if it is further developed to allow for greater degree of multiplicity and a broader conceptualisation of the notions of the “centre of authority” and the translation of the public opinion.

Coastal management accounting for shoreline erosion and coastal flooding requires information about various physical processes that take place over a range of temporal and spatial scales. Field measurements provide information on the past and current coastal environment and statistical tools are used to determine extreme conditions that can lead to damage. However, in a changing climate, these conditions cease to be statistically stationary, making predictions problematic. To assess future conditions, a set of scenarios for greenhouse gas emissions has been defined to project impacts on global oceanographic conditions and sea level rise. This thesis estimates the effect of these global projections on coastal processes off the North Norfolk coast of the UK. A model system is set up to downscale global conditions on to nearshore conditions (wave climate, water level and beach profile), which influence coastal stability and coastal flood risk. The system is based on coupling numerical models for different temporal and spatial scales. The area contains large tidal sandbanks and shore-connected sand ridges. The downscaling procedure accounts for interactions that take place on the upper part of the continental shelf where these large-scale seabed features affect wave propagation, tidal flows and sediment transport. The modelling system is then validated against historical data and then used to compute long-term inshore hydrodynamic characteristics and sediment transport resulting from future projections of climate change and sea level rise. This enables an assessment of extreme inshore wave heights, overtopping discharge rates and their occurrence at a sea defence through extreme joint probability analysis. This modelling assumes a fixed seabed. However, the system includes a sub model for the release of sediment from the cliff erosion, which provides a source of sediment for the maintenance of the offshore sandbanks. The link between the cliff and the sandbanks is demonstrated by computing the residual sediment transport. The model system is also used to assess the impact of offshore sand extraction on coastline erosion. Finally, the system is used to analyse an overtopping and flood inundation event at Walcott in 2007 enabling uncertainties in the predictions to be assessed.

The importance of extremely slow retention and release has superseded the notion that sorption of pesticides to soil is an instantaneous and reversible process. A fraction of sorbed pesticide is also often reported to bind irreversibly to the soil matrix. This has important implications for pesticide mobility and bioavailability. It is essential to understand sorption phenomena to allow accurate prediction of pesticide fate within the soil environment. This thesis describes the result of applying a sequential extraction procedure, based on the principles of isotope or “self-exchange”, to nine pesticide/soil systems. The significance of irreversible sorption in controlling pesticide mobility was assessed using isotope exchange (12C and 14C) to characterise pesticide exchange kinetics in-situ over protracted time-scales. Sequential extraction increased in harshness in the order: isotope exchange < forced isotope exchange < solvent extraction. Three pesticides (one neutral, one basic, one acidic) and three temperate, arable soils (ranging in texture and pH) were studied. A three-site sorption model was developed to further interpret the data obtained. Although results showed the experimental design of the isotope exchange technique was not powerful enough to identify whether remaining sorbed pesticide was participating in slowly reversible or irreversible sorption, the forced isotope exchange procedure was able to provide an indication of amounts of pesticide not participating in exchange between the soil and solution. Under abiotic conditions, only minimal amounts of initial-applied pesticide were found to take part in irreversible binding. Soil combustion quantified irreversible sorption in the order: chlorotoluron (≤ 2.27 ± 0.36%) > prometryn (≤ 1.35 ± 0.60%) > hexaconazole (≤ 0.50 ± 0.06%). Varying the soil composition had little effect on amounts of irreversibly sorbed pesticide, probably due to the small amounts of irreversible sorption observed overall. These results suggest that the vast majority of sorbed chlorotoluron, prometryn and hexaconazole (in the parent form) participated in very slow but reversible binding, a result also confirmed by the three-site sorption model. Pesticide sorption behaviour is a complex process. Although sorption phenomena are still not fully understood, these results provide a greater insight into the significance of irreversible binding for predicting pesticide fate.

This study combines moral panic with the figurational sociology of Norbert Elias to explore how climate change has developed as a social problem. The central argument is that,through combining the short-term focus of moral panic with the long-term focus of Elias, we can examine the interplay between planned and unplanned developments in both the perception and reality of climate change. The first part of the research consisted of discourse analysis of a variety of different texts from 1800 to the present. These were used to explore the long-term development of climatechange as emerging from an ecological civilizing process. The second stage of the research related these developments to moral panics, arguing that the emergence of climate change can only be understood by exploring the interplay between long-term processes and short-term campaigns. The third part of the research explored these historical developments at the individual level, examining the notion of individual ecological civilizing processes. 15 semi-structured interviews were undertaken with climate change ‘activists’ and ‘non-activists’, comparing how their biographical developments related to ecological civilizing processes and moral panics. The final part of the research compared climate change with five other empirical examples of moral panics, to explore the civilizing and decivilizing processes and civilizing offensives that occur before, during, and after the panics. The central aim was to demonstrate the complexity of moral panics, and to aid in the reformulation of the concepts of moral panic and decivilization. Through a synthesis of Elias and moral panic, as applied to the example of climate change, this study aimed to: critically assess the development of climate change; to reassess the concept of decivilization and the relation between civilizing processes and offensives; and to reformulate the concept of moral panic, including suggesting how moral panic research ought to be undertaken.

This thesis sets out to explore some of the key dimensions in the process of socio-technological change inherent in the shift to a low carbon economy. This is done in two parts, the first focusing on theory, the second, empirical case studies. Out of the diversity of interactions between actors, technologies, and policies surrounding this process, one key question emerges: can societies really shift the structure of their economies so fundamentally to achieve a low carbon future within a reasonable timeframe? Chapter One develops an integrated approach to economic and political change to interrogate this question. This synthesizes a review of literature (Part One) examining the role of technology within some of the main theories of economic change in the social sciences. Two broad paradigms are distinguished. First, a paradigm based around the notion of equilibrium, notably the standard welfare approach of neoclassical economics; and secondly, an evolutionary paradigm, which views the economy as a complex adaptive system – such as exemplified by theories of path dependency. This theoretical background provides a broad narrative to frame and inform Part Two of the thesis. First in Chapter Four, socio-technical change is investigated in the context of the diffusion of energy efficient lighting in Germany. This study investigates the relationships between human behaviour and attitudes, lamp technology and the evolving nature of institutions, to provide a framework with which to consider the contentious issue of individual freedom versus government control in the politics of change to lower-carbon emissions. In Chapter Five, the case for the creation of a market for CO2 pollution permits is developed. In making this case, the strengths and weaknesses of emissions trading are compared and contrasted with other policy instruments and the broader political economy of the various policy options discussed. Chapter 6 builds on this to examine the political economy of implementing an emissions trading scheme in Australia and the impact the Kyoto Protocol has had on domestic politics and GHG mitigation. Chapter Seven continues with the theme of building ‘a political ecology of the state’ by investigating the politics and economics of greenhouse gas mitigation in Russia. Finally, Chapter Eight recapitulates the aims, nature and conclusions of this research and draws out its implications for policy as well as mapping out some areas for further research. In particular, the need to bring a greater sense of politics back into the study of the economy is highlighted as a vital part of building a renewed, more sustainable economic paradigm in the wake of the financial crisis and, as a way of strengthening the connection between social values and market outcomes.

The EU has, for a long time, portrayed itself as an international leader on climate change. Previous studies have tended to focus on the characteristics of EU leadership, but have failed to examine the extent to which EU leadership generates “followership”. Going beyond these existing approaches, this dissertation analyzes not just EU attempts at leadership but also the response of two potential followers: China and India. Based on extensive fieldwork, the dissertation explains the pattern of EU engagement and the response to engagement in each case, and makes three key arguments. First, EU engagement was driven by a desire to build the international role of the EU, but also from 2000 onwards in particular by growing normative concern and material interest within the EU regarding combating climate change. The development of engagement was also conditioned by the broader development of EU relations with China and India. Second, EU engagement took the form of institutionalized dialogue and capacity-building projects. These were generally more extensive in the EU-China case; the EU-India relationship was significantly more limited. Both cases were characterized by a lack of EU capacity—particularly the EU-India case—and to some extent by inconsistency and incoherence. Third, the Chinese Government responded through limited normative emulation and limited but growing lesson-drawing through bilateral cooperation in specific sectors. While the Indian Government also responded through limited normative emulation, the principal Indian response was resistance. Moreover, both the Chinese and Indian Governments resisted the EU approach to the international climate change negotiations. This pattern of engagement and significant resistance stemmed partly from the EU’s failure to develop sufficient capacity for effective engagement, but also partly due to significant differences in the way each side has framed the issue of climate change. Based on these findings, the dissertation concludes that while the EU was not entirely a leader without followers, it has acted as a highly restricted leader in its relations with China and India on climate change.

polybrominated diphenyl ethers (PBDEs) are additive flame retardants that have been -widely used globally for the last 30-40 years. In their functional operation, PBDEs are released from parent products when exposed to heat and light in order to retard combustion reactions. The physiochemical properties of PBDEs coupled with widespread use and production has led to ubiquitous environmental contamination by these compounds. In recent years PBDEs have become increasingly well studied and evidence of their toxicity to biota and occurrence in remote and pristine environments has led to the - implementation of legislation to control their use and production. A great many studies have been published on PBDEs, and key concepts are introduced in Chapter 1. However, comparatively little data exists for the UK. Data is lacking on both marine and terrestrial birds of prey; this is disconcerting, given the potential toxicity of PBDEs, as predatory birds have been susceptible to the adverse effects of anthropogenic organic contaminants in the past. Utilising the eggs and livers of two predatory bird sentinel species, the northern gannet (Morus bassanus) and the sparrowhawk (Accipiter nisus), collected as pati of the activities of the Predatory Bird Monitoring Scheme (PBMS), this work aimed to detennine detailed long-term temporal and spatial trends of PBDEs in UK marine and terrestrial systems. In addition, stable isotope residues of carbon and nitrogen were used to identify if changes in the diets of these birds could influence the trends in contaminant residues in their eggs. Furthermore, other potentially confounding factors such as age, sex and body condition were assessed using sparrowhawk livers - a matrix which allowed for the PBDE contamination in male sparrowhawks to be characterised. The findings of the studies conducted as part of this thesis are presented in Papers IIV and discussed collectively in Chapter 2. Methodologies are provided in Papers I-IV and supplemented by Appendix 2. Other POPs, for which data is presented in Paper 4, are discussed in Chapter 1 and Appendix 3. Contributions to relevant studies regarding PBDE toxicity and trends in UK air are presented in Appendices 4 and 5. Key conclusions and recommendations for further work are given in Chapters 3 and 4.

The increased growth of wildlife tourism in Kenya over the last few decades has placed increasing demand and attention for the development and subsequent delivery of sustainable tourism. Today ecotourism ventures are perceived by many as a solution to the negative impacts of "traditional" wildlife tourism and thus a way to achieve ecologicalsustainability within the industry. To date however, there has been no attempt to qualifyand quantify any possible wildlife impacts of ecotourism - the basis of this research, usingthe Mara Ecosystem as a case study. Using WildKnowledge© software, this research recorded biotic and abiotic data from wildlife tourism developments of various sizes and assessed their anthropogenic impacts upon key ungulate species in the ecosystem over a three year period. The findings of this aspect of the research indicate that the effects of the tourism industry on wildlife are highly species specific. In particular Buffalo were most affected by differences in tourism seasonal variability (X2=5.040, df=l, p=O.025), distance to developments (X2=23.341, df=l, p=O.OOO) and group size (X2=7.998, df=1, p=O.005) between the different lodge types. In contrast, waterbuck and eland displayed similar patterns of disturbance irrespective of lodge type or tourism seasonal variability. Using historical species count data spanning a twenty year period, kernel density maps were constructed to demonstrate spatial changes in ungulate density and distribution patterns in relation to tourism growth. The resulting density maps revealed that while the national reserve offered a measure of security to wildlife, many ungulate species still heavily utilised their historical dispersal areas in the community lands. Interestingly, despite the tourism related land use changes demonstrated in the Mara's landscape, some species e.g. eland, displayed an increase in range size - to 4s0.5km2 in 2010 from 399.Skm2 in 2005 following the creation of wildlife conservancies in the surrounding ranches. Constructing site suitability models, the research explored how GIS modelling techniques can be employed to identify suitable locations for tourist accommodation, without compromising the ecological integrity of the wildlife areas where these facilities will be located. Employing two different bed occupancy models (conservancy model; 350 acres/bed and a current model; ; 174 acres/bed, derived from existing facilities), the Mara Ecosystem's ability to accommodate further tourism growth at low ecological cost was demonstrated. Application of the highest suitability criteria to select potential development sites revealed two suitable locations. A further 54 locations were identified as suitable for ecocamps and ecolodges on application of the second highest site selection suitability criteria. Importantly, the models employed clearly demonstrate that the majority of future ecotourism facilities be located outside the National Reserve in the group ranches if they are to have limited wildlife impact, as over-utilisation of any single sections of the ecosystem will lead to resource depletion and localized species loss. The results presented highlight the need for a more integrative approach to ecotourism provision. The utility of GIS based models to project the impacts of human disturbances on wildlife populations under different tourism scenarios is reinforced by this research. These suitability models are easily modified and can therefore be used under different planning scenarios in other wildlife areas in Kenya and the region. It is therefore hoped, that the results from this study will influence policy direction for tourism planning in wildlife areas for the Mara and other ecosystems, and be used to complement the country's tourism and wildlife bills which are about to be passed into law. This research concludes that although ecotourism plays an important role in environmental conservation, its ecological impacts on wildlife in receiving environments can be significant and should be a primary consideration in deciding upon the efficacy of individual proposals.

Geoengineering, intentional large-scale manipulation of the Earth-system, has been proposed as a means to ameliorate the impacts of global warming. There are two approaches; Carbon Dioxide Removal (CDR) geoengineering which would reduce C02 concentrations and address the cause of climate change, and Solar Radiation Management geoengineering which would cool the planet by reducing the amount of sunlight absorbed by the planet without affecting CO2 concentrations. This thesis reviews geoengineering and investigates the direct and indirect climate effects of SRM geoengineering. The sunshade geoengineering scheme, which would reduce the solar insolation, is investigated in depth in this thesis. Sunshade gcoenginecring may be implemented at a range of C02 concentrations and it would also offer control over the amount of insolation that reaches the planet. Both of these aspects of sunshade geoengineering are investigated using a climate model and it is found that sunshade geoengineering would ameliorate most of the effects of elevated C02 but would cause heterogeneous changes in climate; globally reducing precipitation and leaving many regions with a climate markedly different from the pre-industrial. The regional climate effects of sunshade geoengineering are found to vary linearly with both the solar insolation reduction and the C02 forcing applied. An off-line ice-sheet model is used to investigate the indirect climate effects of different strengths of sunshade geoengineering on the Greenland Ice-Sheet at quadrupled CO2 levels, to determine whether sunshade geoengineering could stabilize the ice-sheet and reduce sea-level rise. It is found that the ice-sheet would eventually collapse at quadrupled C02 levels but that strong sunshade geoengineering can stabilize the entire ice-sheet or at weaker implementations, part of the ice-sheet could be maintained. A comparison is made between the urban, crop and desert surface albedo geoengineering schemes, which would have a highly heterogeneous radiative forcing effect, and sunshade gcocngineering, which would have a more homogeneous radiative forcing effect. This comparison shows that regional geoengineering forcing, if it is relatively weak, may provide local and regional cooling and other benefits but for stronger land albedo forcing there are large shifts in precipitation, including substantial reductions in monsoon precipitation, which could prove to be more harmful than the effects of global warming. Finally, to determine the robustness of the results in this thesis, a perturbed parameter ensemble is developed, tested and then used to investigate the effects of parametric uncertainty on the sunshade geoengineering climate effects. The perturbed parameter results agree with much of what was found in other parts of the thesis about sunshade geoengineering but finds that there is uncertainty in the resid- ual warming at the poles, the magnitude of the northward shift of the ITCZ, and that the standard climate model may have overestimated the effectiveness of sunshade geoengineering at maintaining the Greenland Ice-Sheet. Overall, I find that SRM geoengineering could offer a considerable amelioration of the impacts of global warming; however, the climate would differ substantially from a low-C02 climate, and there would be winners and losers as a result. Regional SRM geoengineering would have very heterogeneous climate impacts, potentially causing large problems but could offer a large degree of control over the climate. 'Whether the political risks that control over the climate could bring would outweigh the potential climate benefits, is an open question.

The components of natural water can be divided into three categories: dissolved, colloidal and particulate phases. The colloids are small particles with at least one dimension between 1.0 nm and 1.0 m (IUPAC); they do not sediment when suspended in “solution”. The small size of colloidal particles causes this fraction to have a large surface area with potential to bind significant amounts of trace metals and organic pollutants and also allows colloids to migrate over long distances potentially increasing the spread of the contaminants. To better understand the behaviour of colloidal matter in natural waters, engineered spherical silica colloids of known size were made and chemically labelled so that the colloids can be sensitively tracked through the fractionation process of analytical filtration. The labels used to date have included the toxic metalloid arsenic and the fluorescent compound Rhodamine B, which had also been used to improve sensitivity. The behaviour of engineered labelled colloidal sols has been investigated during the preliminary filtration study in the laboratory. Artificial colloidal sols of the silicas in water were investigated to see how their filtration, employing a sequential filtration of a water sample through 1.6 (or 8 m) and 0.1 m cut-off filters, influenced a measurement of arsenic. The content of the filters after filtration were investigated by scanning electron microscopy and analysed for arsenic using atomic absorption spectroscopy. Ca. 50% and 65% of the silica particles were found on the large pore filters (1.6 um and 8.0 um filter), providing evidence of the aggregation and clogging effects on the fibre filter. The analysis of the Tamar estuary water samples revealed substantial amounts of arsenic, attributed to drainage from mining activities. Colloidal arsenic was found along with dissolved and particulate arsenic in freshwater. However, the saline water samples showed the arsenic content to be distributed mainly in the particulate and dissolved fractions. A suggested explanation of this phenomenon is that aggregation of colloids took place in the presence of saline water and therefore most of the colloidal arsenic was collected with the particulate fraction. Finally, a study of Southampton Water and Dart waters was performed by adding engineered colloidal particles to explore the aggregation of colloids in water of different salinity. Unfortunately, experimental problems prevented a definite verification of the influence of salinity in this case

The unique properties which make cerium dioxide (ceria) nanoparticles (NPs) so useful in e.g. catalytic applications, pose a real risk to environmental systems and species alike. Increasing our knowledge of ceria NP characteristics in a range of aquatic systems was a contributing theme of this thesis. Nano-ceria particle sizes (dH) were found to significantly change due to adjustments in media composition. The addition of Suwannee River fulvic acid to an aquatic media decreased dH up to 88%, significantly increased the negative charge measured from zeta potential (ζ) and increased Ce dissolution by 2%. The presence of test biota significantly increased dH up to 80%, further increased the ζ negative charge and increased Ce dissolution up to 63%, predicted as being due to the presence of exudates. Nanotoxicological investigations using P. subcapitata showed a convincing size-dependent toxicity to well-defined synthesized nanoceria particles. EC50 values of 5 nm to 35 nm ceria particles (0.013 mgL to 0.8 mgL respectively) showed between 600 and 10 fold increases in toxic response compared to commercial nano-ceria particles (EC50 8 mgL). EC50 of 5 nm and 35 nm ceria particles showed significant metabolic differences compared to controls indicating a cellular response of P. subcapitata as a function of nano-ceria size and dose. Although metabolomic extraction methods are sensitive to cell density and temperature changes, metabolomic analysis has huge potential in future environmental nanoecotoxicological applications using P. subcapitata. It was evident from this study that further work is still required to help develop methods of NP characterisations under environmental conditions with a necessity for a future NP modelling protocol.

PBDEs were detected in all air and dust samples. The PBDE congener profile in both outdoor and indoor air samples from Thai e-waste storage facilities and homes was dominated by BDE-47 and 99, whilst the predominant BFRs in all dust samples from Thai e-waste storage facilities were BDE-209, BDE-208, BDE-207, BDE-206, BDE-197, BDE-183, BDE-99, BDE-47 and DBDPE. Furthermore, BDEs 99 and 47 were the most abundant congeners in all dust samples from Thai houses and cars and UK homes. Under realistic high-end scenarios of occupational exposure to BDE-99 via dust ingestion, workers in Thai e-waste storage facilities were exposed above a recently-published Health Based Limit Value for this congener. For non-occupational exposure, under a high-end exposure scenario, the exposure to BDE-99 of such Thai children via dust ingestion is either very close to or in exceedance of the HBLV. PBDE levels in most of the areas monitored within the same rooms were not statistically significantly different. Similarly, concentrations of PBDEs in the majority of rooms within the same houses were not statistically significantly different between rooms. Possible dilution of PBDE levels in dust with increasing dust loadings has been identified in a small number of rooms.

Metal contamination in groundwater aquifers poses risks to human health as well as other life forms. Previous laboratory experiments have demonstrated that bacteria found in geologic settings like aquifers are likely to adsorb metal contaminants and attenuate metal migration. However, as bacteria can also migrate through the groundwater aquifer a better understanding of the combined effect of these two processes is required. The aim of this laboratory study was to a) explore the affinity bacteria exhibit towards metals and porous media of varying composition, b) investigate the effect of mineral and solution composition on the bacterial filtration and c) use the combined data to predict the impact of microbes on metal mobility in porous media. Pantoea Agglomerans was used as a model bacterium while column materials consisted of quartz sand and iron-oxide coated sand (IOCS). Bacteria were characterised using potentiometric titrations to identify the type and concentration of sites present on their bacterial wall. Particular attention was paid to the effect of kinetics of proton and metal adsorption due to the variable contact times that solutions have with bacteria in columns. It was found that increasing the contact time between cell surfaces and protons during potentiometric titrations resulted in less reproducible results. This was due to the release of cell exudates under high pH conditions rather than cell death. Exudates were also found to adsorb protons. Moreover, zinc adsorption onto cell surfaces is higher after 60 to 90 minutes of contact time, while there is a decline in adsorption for longer contact times due to release of cell exudates in the solution. Stability constants for the adsorption of zinc onto cell surface sites, quartz and IOCS materials were determined through batch adsorption experiments, providing a mechanistic explanation of the adsorption process. Reactive transport models incorporating kinetics and surface complexation are developed to describe zinc movement through packed columns. Batch kinetic studies showed that significant Zn sorption to IOCS takes place gradually during the first two hours of contact time. Adsorption continues to take place at a slower rate for an additional 10 hours. This kinetic effect is manifested also during flow-through experiments (column dimensions: length 0.12 m, diameter 0.025 m) with a Darcian velocity 6.1·10-3 cm s-1, which is comparable to natural groundwater flow rates through sand porous media. A pseudo-second order kinetic adsorption model is combined with a numerical advection dispersion model for the first time to predict Zn transport. Model output results are of mixed quality as the model cannot successfully describe contaminant arrival time and breakthrough curve shape simultaneously. Moreover, a mechanistic surface complexation reactive transport model is capable of predicting Zn sorption under varying pH conditions demonstrating the versatility of mechanistic models. However, these models do not account for kinetics and therefore they are not intended to fit the dispersion of the contaminant due to kinetic effects of adsorption. Experiments in mixed zinc/cell systems demonstrate that transport through IOCS is dominated by the adsorption to the porous medium. This is consistent with the batch surface complexation predictions for the system. Adsorption to bacteria is reversible and zinc is stripped from the cells and redistributed onto the IOCS. Adsorption onto cells becomes significant and plays a role in mobile metal speciation only once the column is saturated with zinc.

Heterogeneity of contaminants in soils can vary spatially over a range of scales, causing uncertainty in environmental measurements of contaminant concentrations. Sampling designs may aim to reduce the impact of on-site heterogeneity, by using composite sampling, increased sample mass and off-site homogenisation, yet they could overlook the small scale heterogeneity that can have significant implications for plant uptake of contaminants. Moreover, composite sampling and homogenisation may not be relevant to target receptor behaviour, e.g. plants, and studies, using simplistic models of heterogeneity have shown that it can significantly impact plant uptake of contaminants. The alternative approach, to accept and quantify heterogeneity, requires further exploration as contaminant heterogeneity is inevitable within soils and its quantification should enable improved reliability in risk assessment and understanding variability in plant contaminant uptake. This thesis reports the development of a new sampling design, to characterise and quantify contaminant heterogeneity at scales, from 0.02m to 20m, using in situ measurement techniques, and 0.005m to 0.0005m, using ex situ techniques. The design was implemented at two contaminated land sites, with contrasting heterogeneity based upon historic anthropogenic activity and showed heterogeneity varying between contaminants and at different spatial scales, for Pb, Cu and Zn. Secondly, this research demonstrates how contaminant heterogeneity measured in situ can be recreated in a pot experiment, at a scale specific to the plant under study. Results, from 4 different plant species, demonstrated that existing simplistic models of heterogeneity are an inadequate proxy for plant performance and contaminant uptake under field conditions, and significant differences were found in plant contaminant concentrations between simplistic models and those based upon actual site measurements of heterogeneity. Implications of heterogeneity on plant roots were explored in the final experiment showing significant differences in root biomass between patches of differing contaminant concentrations.

Urban areas are highly dynamic and diverse systems and the interactions and networks within an urban area are, at present, only partly understood, although some of the most important impacts on human health occur in these areas. It is essential, therefore, to develop a deeper understanding of these urban dynamics and processes especially with regard to exposure and health risk assessment. This thesis describes the development and application of an urban SImulation for ENvironmental health Analysis (SIENA). SIENA provides a controlled, simplified urban environment to develop and test spatial epidemiological concepts and models, to simulate processes and interactions relating to environmental exposure and to explore theoretical and methodological problems in the spatial analysis of environmental health. The development of the simulated urban system focuses on identifying and quantifying fundamental processes and inter-dependencies in the structure of urban areas in Great Britain. Twelve cities are chosen as sample cities and their spatial data structure (topography, transport network, land cover) and relationships between these structures and the urban population are statistically analysed. Based on the results of the statistical analysis SIENA is developed within a Geographic Information System (GIS) using probabilistic models and spatial analysis tools. Beside the identified core structure, topography, transport network, land cover and population, additional data such as traffic flow, air pollution monitoring networks or emissions from industrial sources amongst others are modelled and incorporated into SIENA. To demonstrate the potential of the simulation, SIENA is applied in two case studies both focusing on the misclassification of human exposure to urban air pollution. The first case study explores the representativeness of various air pollution monitoring networks and the resulting implications for exposure assessments. For the second case study, personal exposure is simulated within SIENA and then compared to the use of a location-based exposure proxy and the potential exposure misclassification spatially analysed.

Research was conducted to evaluate the potential of chitosan, a fishery waste-based material, and its derivative cross-linked chitosans, as soil amendments for the remediation of metal contaminated land. This research comprised modification of chitosan followed by a characterisation study, a batch sorption study, two pot experiments and a biodegradation study. Chitosan was modified with three cross-linking reagents, namely glutaraldehyde (GLA), epichlorohydrin (ECH) and ethylene glycol diglycidyl ether (EGDE). The characterisation study used X-ray diffraction (XRD), scanning electron microscopy (SEM), energy dispersive X-ray analysis (EDX) and Fourier transform infrared spectroscopy (FTIR) methods to investigate the effect of cross-linking treatment on the surface and physical properties of chitosan, the effect of metal interaction on the surface properties of chitosan and cross-linked chitosans, and the binding mechanism(s) of metal ions onto the chitosans. Cross-linking treatments on chitosan enhanced its chemical stability in acidic media and increased its BET surface area. Metal interaction reduced the crystallinity and changed the surface morphology of the chitosans. FTIR analysis revealed that the complexation of metal ions was through dative covalent interaction with the amino and hydroxyl groups of the chitosans. The batch sorption study evaluated the ability of chitosan and cross-linked chitosans to bind heavy metals. The effects of contact time, initial metal concentration and background electrolyte on metal binding were assessed. The binding behaviour was described by several kinetic and isotherm models. The maximum binding capacity (Q) values, estimated using the Langmuir isotherm model for the chitosans were comparable with other low-cost sorbents reported in the literature. The sorption-desorption study showed that the chitosans were able to retain metal ions on their surfaces, even at dilution factor of x11. The pot experiments evaluated the effectiveness of chitosan and chitosan-GLA in immobilising heavy metals in the contaminated soil. Their effects on plant growth and metal accumulation in plant tissue were determined using Lolium perenne (perennial ryegrass) and Brassica napus (rapeseed). For perennial ryegrass, the results were dependent on the rate of addition of the chitosans. Low application rates (up to 1% w/w) resulted in an increase in metal uptake, whereas 10% (w/w) addition decreased metal uptake. For rapeseed, metal uptake was decreased at all rates of application of chitosans. The ammonium acetate extractable metals in soil decreased following application of chitosan and plant growth. The biodegradation study measured microbial breakdown of the chitosans in both non-contaminated and contaminated soils. It was estimated that a longer period is required to complete the breakdown of the cross-linked chitosans (up to approximately 100 years) than unmodified chitosan (up to approximately 10 years). The influence of biodegradation on the bioavailable fraction of heavy metals in soil was studied concurrent with the biodegradation trial. It was found that the binding behaviour of chitosan for heavy metals in soils was not affected by the biodegradation process.

Many recent studies have highlighted the substantial health-related impacts of particle number (PMno) rather than particle mass. The aim of this study is to determine the correlation of trace gases with PMno, to identify the chemical composition of particle different sizes and to predict the NOx and PMno over Yanbu Industrial City (YIC). Trace gases (NOx, SO2, H2S, O3, CO), PMno with diameter (7nm-10μm), traffic and meteorological parameters were measured at three sampling sites in YIC. The maximum PMno (333,971 cm-3) at downwind site#1 was about 2.5 times higher than that (123,842 cm-3) at upwind site#2 and about 1.2 times higher than that (263,572 cm-3) at downwind site#3. The average PMno distribution at downwind sites consisted of one distinguishable mode (nucleation mode<20nm) whereas the upwind site had two modes (the nucleation and the accumulation modes). The correlation of PMno with NO/NOx (r>0.7) are generally stronger than with NO2 at sites#1 and 2, whereas for site #3 the correlation between PMno with NO2/NOx are better than with NO. PMno has generally either weak or poor correlation with SO2 and CO, respectively. Particle samples of different sizes (7nm-10?m) were chemically analysed using an ion chromatograph (IC) for inorganic ions and inductively coupled plasma mass spectrometry (ICP-MS) for trace metals at site#3. The ionic analysis revealed that sulfate and ammonium was mainly present in particle of size < 0.38μm while nitrate and chloride was mainly present in particles of size > 0.38μm. Non-sea salt sulfate was dominant in all particle sizes compared to the marine sulfate which is minor. The total sulfate and nitrate contributed 50.3% and 24.4% of the total ionic mass respectively followed by chloride (13.3%) and ammonium (10.6%). The trace-metals analysis results indicated that Na represented more than 94% of the total mass and the contributions of the remaining metals (Al, Sr, Zn, V, Cr, Fe, etc) were about 6%. A further part of this study consisted of the coupling of the WRF/CALMET system with the CALPUFF model, which was applied to predict NOx and PMno concentrations. The WRF model was employed to generate the meteorological input data for CALMET. WRF predictions were evaluated with surface data and upper air profiles using RASS/SODAR and radiosondes. WRF tends to underestimate the surface temperature on average with biases of up to -3.4°C and also underestimates temperature profiles with average biases ranging between -2.7 and -5.2oC when compared to the RASS profiler, but with a lower bias (< -2.4°C) when compared to radiosonde profiles. The mean wind speed bias for the majority of the cases was close to the benchmark of ±0.5m/s, but the mean wind direction bias for half of the cases exceeded the benchmark of 10o. It was concluded that WRF predictions can be used for air dispersion modeling to produce reasonable outputs. NOx predictions by CALPUFF showed that the contribution of the traffic to the highest concentrations during the nighttime was up to 80%, but after sunrise the contribution from industries became higher (up to 70%). The highest predicted NOx concentration (~313μg/m3) was much lower than the national ambient standard (660μg/m3) and the community area is affected much by industries during mid-morning hours when the wind shifting from land breeze to sea breeze. The fractional bias (FB) ranged between -0.1 and 1.06 indicating that the model tends to under-predict the NOx observations. PMno predictions of two sizes (7-40nm and 7nm-10μm) were derived based on the NOx predictions. All FB values were ranged between -0.1 and 0.5. It was concluded that PMno predictions were generally better than those of the NOx due mainly to adding the background term (intercept) for the PMno predictions.

Osmoregulation is an essential process to maintain water and ionic balance and when euryhaline fish move between freshwater and seawater environments as part of their life cycle this presents additional osmoregulatory challenges. Migrating fish can be exposed in both environments to pollutants such as endocrine disrupting chemicals (EDCs) that include natural hormones (e.g. 17β-estradiol; E2), synthetic hormones (e.g. 17α-ethinylestradiol; EE2), and industrial chemicals (e.g. nonylphenol). The focus of this thesis was to study the effects of different categories of EDCs on the osmoregulatory functions of euryhaline fish such as three-spined sticklebacks (Gasterosteus aculeatus) and rainbow trout (Oncorhynchus mykiss). Osmoregulatory variables (such as osmolality, water and ionic content) were compared in plasma and tissues (white muscle and carcass) of rainbow trout. This validated the use of specific tissue parameters as a surrogate of plasma responses to various osmoregulatory challenges. Waterborne exposure to 17α-ethinylestradiol revealed differential sensitivity of vitellogenesis in the three-spined sticklebacks (no induction) and rainbow trout, but had a significant effect on calcium homeostasis in both species. Intraperitoneal implants of 17β-estradiol reduced CaCO3 production and apparent water absorption in the intestine and increased in tissue calcium stores of seawater-acclimated trout, but fish were able to compensate and showed no overall osmoregulatory disturbance. Waterborne exposure to nonylphenol in freshwater trout was also investigated, but no effects on osmoregulation were found up to 2 ng/l. Overall, estrogens can affect osmoregulation differentially in euryhaline fish species, and sometimes at EDC levels lower than the threshold for reproductive effects (i.e. vitellogenin induction).

It is now well established that a wide range of natural and anthropogenic chemicals present in the aquatic environment have the potential to disrupt the endocrine system of many organisms. In fish, many of these effects appear to be of a feminising nature, including stimulation of vitellogenin production and induction of intersex. In piscivorous birds these so called endocrine disrupting contaminants have been shown to impair reproduction, influencing reproductive behaviour, sex ratio, eggshell thickness and reproductive success. The effects seen in fish have been associated with high levels of oestrogenic activity in the effluent from waste water treatments works (WwTWs), but few studies have focused on the effects of WwTWs effluents on birds. In this thesis, the effects of effluents from WwTWs on fish and birds were investigated in the Tamar catchment, SW England. The work spanned making detailed assessment on the oestrogenic and anti-androgenic activity of 3 WwTWs effluents, using a variety of water sampling techniques and applying both recombinant yeast oestrogen screen (YES) and recombinant yeast androgen screen (anti-YAS) bioassays to quantify the different hormonal activities. A survey was undertaken of the hormonal activities at 13 sites to determine concentrations of contaminants in the surface waters throughout the Tamar catchment, using both recombinant yeast screens and targeted analytical chemistry for specific pollutants (LC/MS-TOF and GCMS). An ELISA was developed to quantify vitellogenin (VTG) in the bullhead (our study fish sentinel) as a biomarker of oestrogen exposure, and evidence of endocrine disruption was investigated in wild populations of the bullhead, Cottus gobio and the dipper, Cinclus cinclus. Macroinvertebrates from upstream and downstream of three WwTW's effluent discharges and from three sampling sites were also sampled as an index of overall water quality in the Tamar catchment, and as an assessment of food availability for the bullheads and dippers. For the studies on the hormonal activities in three WwTWs in the Tamar catchment, samples were collected by both spot and passive sampling; passive samplers (in replicate) were placed in the effluent discharges for a three week period, and collected on days 7, 14 and 21, spot samples were taken simultaneously. Measurement of total oestrogenic and total anti-androgenic activity was conducted using the YES and anti-YAS, respectively. Spot and passive samples were collected from 13 sites within the Tamar catchment (sampling sites were >2 km downstream of effluent discharges). Additionally, liquid chromatography mass spectrometry time-of-flight (LC/MS-TOF) was used to measure the concentration of oestrone (E1), 17β-oestrodiol (E2) and 17α-ethinylestradiol (EE2) in each sample. Gas chromatography mass spectrometry (GCMS) was used to measure the concentration of individual PBDE and PCB congeners in the spot samples only. Levels of oestrogenic and anti-androgenic activity observed in the WwTWs effluent were comparable with those measured in effluents in the UK and in other countries. Surface waters of the Tamar, away from the WwTWs effluent discharges, contained very little oestrogenic activity (<1.1 ng E2 EQs L-1), and anti-androgenic activity was undetectable. Quantification of oestrogenic activity using passive samplers showed an increasing amount of total oestrogenic activity between days 7 and 21 when measured by the both the YES and LC/MS-TOF. Low levels of PBDE congeners 47, 99, 100, 138 and 153 were detected in the spot samples taken from the Tamar catchment, with BDE 47 being the most abundant. In contrast PCBs were undetectable. Neither PBDEs nor PCBs were detected in any of the extracts from the passive samples. No assay was available to measure VTG (one of the most widely used biomarkers of oestrogen exposure in fish) in the bullhead and so an enzyme linked immunosorbant assay (ELISA) was developed for application to studies on wild bullheads in the Tamar catchment. The bullhead vitellogenin (bh-VTG) ELISA was developed successfully, and proved to be sensitive and robust, with a detection range between 10.5 and 300 ng bh-VTG mL-1 (undiluted), comparing favourably with other fish VTG ELISAs. Plasma VTG concentrations measured in male bullheads (collected from the same sites as for the water samples) ranged from below the limit of detection to 990 ng bh-VTG mL-1. Whether these upper levels in the range reflected VTG induction was difficult to conclude. Because of this controlled caged exposures with bullheads and trout were used to assess the relative levels of oestrogenicity in two key WwTWs effluent discharges and to determine the response sensitivity of the bullheads (and trout) to those effluents. These controlled exposures found no responses in plasma VTG in bullheads (ranging between 126 and 934 ng bh-VTG mL-1) suggesting a lack of sensitivity for VTG induction. This was supported by the inability to induce VTG in fish held in the laboratory and treated with steroidal oestrogens. For the effluent exposures on the caged rainbow trout, it was also found that there was no significant induction of VTG, a species normally sensitive to oestrogens. These findings may indicate that the fish were highly stressed due to the river being in spate and the movement of the cages during the controlled exposures. It may also be the case, however, that the use of immature female rainbow trout with a highly variable baseline plasma VTG concentration may prevent any detection of a response. There were no signs of sexual disruption in any of the gonads analysed from either male or female wild bullheads, demonstrating that any hormonal activity present in the catchment away from the WwTWs effluents was not sufficient to induce adverse effects on reproductive development. An interesting feature noted in the male testes of the bullheads was the presence of spermatid masses, which have been recorded in 10 other Cottidae species, but not previously in the bullhead. For the studies on dippers, eggs were collected from the nests of breeding dippers to measure for sperm numbers and morphology from sperm trapped in the perivitelline membrane (PVM), and the yolks were analysed for PBDEs, PCBs and organochlorine pesticides (OCPs) by GCMS, for E1, E2, and EE2 by LC/MS-TOF. Eggs of the dipper were collected from nests at the 13 sampling sites, plus an additional three sites and over three years of field study. The number of sperm trapped in the PVM ranged between three and 188, with a mean of 68.78 ± 8.78 SE. Dipper sperm had not previously been characterised, and was found to be similar to other passerine sperm, in that the head was helical, complemented by a mitochondrial helix or keel, which continued in a spiral around the flagellum. Sperm were classed as ‘abnormal’ if they did not adhere to this typical structure. No assessment of motility could be made in relation to the structural abnormalities seen. Contaminants in the dipper eggs were dominated by BDE 99, an unusual result considering the dippers aquatic lifestyle. PCB 153 was the most common PCB, and p,p’-DDE was the most abundant OCP; all other pesticides tested were below the limit of detection, as were the levels of all three steroid oestrogens. There was inter- and intra-nest variability between contaminant burdens in all eggs as well as the number of sperm trapped in the PVM, but there was no relationship between sperm number and the level of contaminant loadings in the eggs. There were no correlations between contaminants and oestrogenic activity measured in the water samples, and plasma VTG concentrations in bullheads or contaminant loadings in eggs, or indeed sperm number. Analysis of macroinvertebrate assemblages proved that the surface waters of the Tamar catchment were of ‘very good’ quality, even in close proximity to WwTWs effluent discharges.

During the 1960s-1980s antifouling applications containing the organotin tributyltin (TBT) were applied to craft on the Norfolk Broads, leaving a legacy of contaminants in sediments. Previously, no research had been undertaken to investigate the implications that this legacy may have for the ecological integrity of the Norfolk Broads aquatic ecosystem. Eight sites in the Norfolk Broads that represented a gradient of contamination (as measured by sediment TBT concentrations) were selected. Contamination was evident in invertebrates and fish but was lower than sediments, as total organic carbon and species specific metabolic capacity for TBT controlled bioavailability To examine TBT impacts at the community scale, novel metrics were applied to food webs defined by stable isotopes of carbon and nitrogen. Two metrics were reduced in response to increasing TBT contamination, suggesting simplification of food webs along the contaminant gradient; where loss of key food web properties such as trophic diversity and shortened food chain length could reduce resilience to further system perturbations. I hypothesised that chironomids emerging from sites contaminated with organotins would carry with them an organotin burden, which would be reflected in terrestrial predators such as spiders via trophic transfer. A combination of spider and chironomid stable isotopes (principally δ 13C) and isotope mixing models indicated considerable chironomid contribution to spider biomass at all four sites (34-88%). Subsequent organotin analyses revealed consistent low level, butyltin (di-butyltin; DBT) contamination in chironomids and spider predators from the most contaminated site.

The treatment of wastewater and monitoring of its toxicity is essential before discharging it to the environment. This study focuses on assessing the toxicity of wastewater following treatment using the electrochemical peroxidation process (ECP). Three categories of low-cost toxicity assays were used based on plant cells, microorganisms and invertebrates, all of which do not require ethical approval or a special licence. In addition, a novel cost-effective device was developed for assessing wastewater toxicity at low concentrations. In Chapter 2, the problem of high turbidity of the ECP-treated samples is addressed, by accelerating particulate settling of the existent compounds. This was achieved by storing the ECP treated samples at low temperatures. This is an essential step for enhancing the clarity of the processed samples in order to improve the performance of the toxicity assays.