Spatial and temporal trends of dissolved organic matter (DOM) were investigated in the Lower Kinabatangan River, Sabah, Malaysia over the period 2008-2012. The objectives were to: i. quantify DOM in areas of the catchment dominated by oil palm plantations; ii. characterise DOM quantity and quality in waters draining three contrasting land use types (oil palm plantations, secondary forests and coastal swamps); iii. characterise and interpret DOM quantity and quality in the main stem of the Kinabatangan river according to depth; and iv. infer differences in water movement through the catchment. Optical parameters, including fluorescence excitation-emission matrices (EEMs) and ultraviolet absorbance spectroscopy (UV-vis); and Parallel Factor Analysis were used throughout the investigation. The research comprised a preliminary catchment-wide study (225 samples) and concentrated fieldwork campaigns (510 samples). The results indicated the dominance of peaks C and M in waters from the oil palm plantations and coastal swamps respectively. The relative loss of terrestrial derived peaks could indicate progressive DOM degradation from the upper reaches towards the estuary. Results also showed DOM was transported back to the main river, as dominated by fluorescence index peak A/peak C, particularly in the coastal swamps. DOM characterisation with depth in the river, showed the dominance of peaks C and M (relative to terrestrial and microbial and/or photo-degradation processes) in waters near the riverbed.

This research is united by both geographical area, principally the Vale of York, and methodology, stressing the use of insect remains in interpreting archaeological environments. Firstly the Cover Sands of North Lincolnshire and the Vale of York are considered. A terminal Devensian age is suggested for the majority of this extensive aeolian deposition and evidence for mode of origin and palaeoenvironment is discussed, with particular regard to insect faunas from within the Sands at Flixborough and Messingham, near Scunthorpe. A brief examination of the nebulous Creswellian industry in relation to the Sands is followed by the study of Mesolithic and Neolithic artifacts from on top of the Cover Sands at Misterton Carr, Nottinghamshire, and the affinities of the earlier part of this assemblage are considered with some current archaeological models of the palaeoenvironment. The trackway beneath Thorne Moor provides an opportunity to examine a local Bronze Age environment and the problems of the genesis of this lowland raised bog and also to discuss more widely the insect fauna of undisturbed forest and the effects of human interference, particularly forest clearance, upon it. The Roman sewer in York contrasts with the largely natural environments examined previously and the attempt to interpret the slight environmental data obtained leads into an essay upon synanthropic insects and the archaeological evidence for their long association with man. This unwanted alliance provides the means to reinterpret a Roman deposit, the Malton burnt grain, which has been linked with the historical events of A.D. 296. The apparent evidence for barbarian attack in northern England is reviewed and a less histrionic interpretation suggested.

Mussels (Mytilus edulis) are able to bioaccumulatc many chemicals including potential genotoxicants in their soft tissues. Certain genotoxicants damage DNA and other macromolecules via production of reactive oxygen species. Genotoxicants can also interfere with DNA repair processes in the cell. This project examined the potential of such agents to produce oxidative damage in gill of mussels both under laboratory and field exposures. Indigenous mussels from a polluted (New Brighton) and a reference (Llandudno) estuary were collected in 2005-2006 and were examined for DNA damage, lipid peroxidation, glutathione depletion and effects on repair of DNA damage (8-oxo-deoxyguanosine). From the parameters tested, 8-oxodeoxyguanosine levels (assessed using the formamidopyrimidine glycosyJasemodified comet assay) were higher in mussels from the polluted site only during summer whereas repair (cutting) of 8-oxo-deoxyguanosine in DNA was lower in the polluted site at most collection times. Lipid peroxidation varied according to season. Subsequent maintenance of mussels under clean laboratory conditions for one month abolished the differences between sites in most cases for all the parameters. In vivo exposure of mussels to the metals hexavalent chromium and cadmium also verified DNA damage via reactive oxygen species and the suppression of DNA repair mechanisms (towards either 8-oxo-deoxyguanosine or ethenoadenosine) was shown to be a potential contributor to genotoxicity. Overall, mussels were shown to be sensitive to the genotoxic potential of different aquatic pollutants. The study emphasises the need to measure specific oxidative DNA lesions rather than a simple measurement of frank DNA strand breaks and supports the strategy of "recovery" experiments to determine recoverable, field-induced damage to DNA and other macromolecules.

Analytical methods based on gas chromatography in combination with electron capture negative ion/electron ionisation mass spectrometry were developed and validated for the separation and determination of legacy and emerging flame retardants (EFRs) in a wide range of samples including indoor air, dust, diet and human milk. A broad suite of EFRs and legacy flame retardants (FRs) including polybrominated diphenyl ethers (PBDEs) and hexabromocyclododecane (HBCDDs) were determined in indoor air and dust taken from offices and homes in Birmingham, UK. Comparison with previous data, suggests that temporal trends in contamination with EFRs and legacy FRs reflect changes in production and use of such compounds as a result of bans and restrictions on the use of legacy FRs. Using inter alia a simple, single compartment, steady state pharmacokinetic model, human exposure to FRs via air inhalation, dust ingestion and diet was estimated for different age groups and the relative importance of each exposure route to overall exposure assessed under different exposure scenarios. Concentrations of target EFRs were detected for the first time in UK human milk samples (n=35). Human exposure to EFRs and HBCDDs via diet was estimated for a population impacted by a rudimentary e-waste processing area in Vietnam.

The aim of this research was to evaluate the utility of innovative in vitro techniques as an alternatives for human/animal tissues to study the transdermal uptake of organic flame retardants from indoor dust and consumer products. Firstly, we successfully designed and applied an in vitro physiologically based extraction test to provide new insights into the dermal bioaccessibility of various FRs from indoor dust. These investigations revealed the bioaccessible fraction for the brominated flame retardants (BFRs) α-, β-and γ- HBCD and TBBPA to 1:1 (sweat/sebum) mixture to be 41%, 47%, 50% and 40%, respectively, while for the phosphate flame retardants (PFRs) TCEP, TCIPP and TDCIPP, the values were 10%, 17% and 19%. With the exception of TBBP A, the presence of cosmetics had a significant effect (p < 0.05) on the bioaccessibility of our target FRs from indoor dust. The presence of cosmetics decreased the bioaccessibility of HBCDs from indoor dust, whereas shower gel and sunscreen lotion enhanced the bioaccessibility of target PFRs. Secondly, we developed a protocol for studying dennal uptake of legacy and novel brominated flame retardants using two 3D-HSE (three dimensional human skin equivalent tissue) models, EpiDerm™ and EPISKIN™ in compliance with the OECD guidelines 428. Overall, results showed a significant negative correlation between the permeability constant of FRs and their Log K_ow values. We also mimicked real life exposure scenarios by exposing the skin surface in turn to FR-containing dust, reference material plastics and upholstered fabrics. Our findings showed that under such scenarios dermal exposure to FRs was appreciable for UK adults and toddlers. For example, for dust exposure, our estimates of daily intake indicated toddlers to be 10 times more highly exposed than adults in the presence of sweat and sebum. This differential exposure is likely attributable to more dust adhering to toddler's skin and their higher exposed skin surface area to body weight ratio compared to adults.

Over the past few decades, South Korea has experienced economic development and urbanisation, the effects of which have included environmental degradation and social problems. The principles of sustainable development have gained support as an approach to dealing with these issues; and the compact city has been proposed as a means of delivering sustainable development without the sprawl of Western cities. This thesis examines the applicability of the compact city to South Korea, particularly to large-scale developments, through the perspective of sustainable development. The research questions, ‘How and why have urban developments in South Korea been accompanied by compactness?’ and, ‘What implications does this have for sustainable development?’ are examined through two case studies: Yong-in, a city developed by diverse methods; and Se-jong, a city developed as a single new project. The case studies demonstrate that new settlements by high-rise apartments in South Korea have achieved a high degree of compactness, and residents have appreciated their liveability and made them their popular housing choice. The thesis concludes that the compact city in South Korean urban development is not only feasible, but is acceptable to residents; and it suggests a compact city model and strategies applicable in the South Korean context.

A method was developed and validated for GC/MS analysis of PBDEs in a variety of matrices (soil, dust, sediment, and 10 types of foodstuffs), represented by a total of 313 samples. Extensive environmental contamination by PBDEs is shown to arise as a result of improper e-waste handling in Guiyu, China, with open burning and circuit boards shredding operations identified as the most significant sources of PBDEs to soil and sediment. Elevated concentrations of selected key pollutants, including legacy and novel brominated flame retardants (NBFRs), polychlorinated biphenyls (PCBs), and metals/metalloids, were detected in a number of dietary samples from Taizhou e-waste recycling sites, confirming the hypothesis that improper e-waste handling is an important source of toxic contaminants to locally produced foods. Human exposure, of both adults and children, to key pollutants via diet was estimated, with results suggesting that children are particularly exposed to a range of toxic substances through a locally-sourced diet. This was especially evident in the case of PCBs, PBDEs, cadmium, and lead. Concentrations of, and/or routes of human exposure to, several contaminants (e.g., PBDEs in duck eggs, and compound-specific NBFRs in diet originating from Taizhou) are reported here for the first time. Application of a simple pharmacokinetic model to predict human body burden of PBDEs (based on estimated dietary intake) provided predicted PBDE body burdens that compared satisfactorily in most instances with those reported elsewhere in blood of adults from Taizhou e-waste sites.

The UK has an environmental legacy of chlorinated solvent contamination from historic industrial activity. Groundwater in Permo-Triassic Sandstone aquifers has been widely impacted. Future use of this resource requires methods to forecast regional-scale chlorinated solvent risk to groundwater assets. Current methods do not adequately represent chlorinated solvent dense non-aqueous phase liquid (DNAPL) source term behaviour and transient contaminant transport. This research investigates the hypothesis that improvements for regional contamination forecasting methods are possible and necessary. Experimentation with particle-based transport solutions shows that neglect of spatial dispersion is over-simplistic, especially where there are complex interactions between capture zones of different receptors. A fully dispersing Lagrangian solution, dynamic random walk (DRW), is developed that accurately models contaminant migration even with coarse-gridded flow models. For representation of the source term, a review of research into DNAPL behaviour is conducted. It is not feasible to derive a generic model for DNAPL dissolution into groundwater based on readily derived metrics at the regional scale. Therefore, a source term framework is developed that tests multiple conceptual models of DNAPL behaviour and therefore gives a holistic uncertainty analysis. Two case studies, based in historically industrial catchments in Birmingham and Stourbridge, validate the combined use of the DNAPL source term framework and the DRW transport solution. Chlorinated solvent sources are persistent, but careful asset planning informed by these regional risk modelling tools- DRW and the DNAPL source term framework -could allow continued use of solvent-impacted groundwater bodies.

Climate change is altering the phenology of bumblebees in parts of the UK, with worker activity recorded during winter. This presents a unique set of physiological challenges to bumblebees, as they are typically exposed to exclusively summer conditions. The aim of this thesis was to assess the capacity for winter activity and survival in the UK-native bumblebee Bombus terrestris audax (Harris, 1780) (Hymenoptera: Apidae) and the commercially imported B. t. dalmatinus Dalla Torre, 1882 (Hymenoptera: Apidae). Cold tolerance assessments indicated that both subspecies were physiologically ill-adapted to winter temperatures. However, both species were found to undergo Rapid Cold Hardening (RCH); the first evidence of RCH in Hymenoptera. Thermal activity thresholds (CTmin, chill coma and chill coma recovery) were significantly lower in B. t. audax than B. t. dalmatinus. However, only B. t. dalmatinus was able to lower these thresholds as a result of acclimation. This highlights the potential for competition between the subspecies. Field experiments showed a lack of winter-active bumblebees in Birmingham, and an inability of commercial colonies to survive winter. Finally, this thesis presents the first evidence to suggest that sublethal neonicotinoid exposures impair bumblebee activity at low temperatures. Results are discussed in the light of climate change, pesticide use and the bumblebee pollinators in future climate scenarios.

This thesis applies integrative and systemic approaches to gene expression experiments measuring responses to environmental stress. Methods were developed to identify systematic differences in response strength, functional pathway activation, and gene regulatory network structure. Results in three wild killifish populations revealed high population variability at the level of individual genes, consistent with the killifish’s genetic diversity and ability to adapt rapidly to anthropogenic pollution. Despite gene level diversity, modular network structures, patterns of pathway activation, and patterns of gene expression canalization were conserved in the three populations, demonstrating that gene regulatory networks are preserved by selective processes and may constrain killifish adaptation. The presence of arsenic during killifish acclimation to osmotic shock systematically reduced the magnitude of gene expression responses, and reduced coordination between genes that respond to osmotic shock. Results in the water flea suggested that cadmium tolerance is associated with systematically larger gene expression responses to cadmium stress, and greater network coordination among genes that respond to cadmium. In summary, environmentally responsive gene regulatory networks 1) shape the efficacy of biotic and abiotic stress responses, 2) are targeted by toxic effects, and 3) are shaped by selective forces.