The Cenozoic represents the transition from the greenhouse world of the Cretaceous to the ice house world of today. Nonetheless, it was not a steady linear trend from an ice free world to an ice house, and there were several reversals along the way. One such reversal was the Mid Miocene Climatic Optimum (MMCO, 14-17 Ma). Material from the Ocean Drilling Program Site 926 on Ceara Rise in the Equatorial Atlantic Ocean is used to examine two intervals within the MMCO from 16.4-15.9 Ma and 15.7-15.3 Ma. Stable isotopes and trace element ratios in two species of benthic foraminifera, Cibicidoides wuellerstorfi, and Oridorsalis umbonatus, and one planktonic foraminifer, Globigerinoides trilobus are used to reconstruct multiple climatological parameters at 2-4 kyr resolution. Paired Mg/Ca and δ18O measurements from the benthic species examined suggest that sea level varied by as much as 40m during the MMCO. Sea level variability was accompanied by changes in sea surface salinity, as measured using δ18O and Mg/Ca from G. trilobus, which suggests that the Intertropical Convergence Zone (ITCZ) was responding to high-latitude forcing centred upon the Northern Hemisphere. The implication is that significant Northern Hemisphere ice sheets were present during the Middle Miocene, some 13 Ma before their currently held date of inception during the Pliocene. These changes in sea level were accompanied by large changes in benthic and planktonic carbonate saturation states (Δ[CO32-]), which are inferred to be representative of changes to global alkalinity and dissolved inorganic carbon. Changes in global export productivity, as evidenced by benthic foraminiferal accumulation rates and the planktonic-benthic gradient of δ13C, are inferred to be controlling the carbon cycle and atmospheric pCO2ATM during the MMCO. The ITCZ is also inferred to be controlling primary productivity at Ceara Rise. Additionally, the relationship between multiple trace element/Ca ratios and Δ[CO32-] are examined using core-tops taken from the Norwegian Sea. The relationship between Mg/Ca and Δ[CO32-] in C. wuellerstorfi is confirmed by expanding the available holothermal data. Mg/Ca in the benthic species Pyrgo murrhina appears to respond exclusively to changes in Δ[CO32-], and the relationship of U/Ca in P. murrhina to Δ[CO32-] is the opposite of that seen in C. wuellerstorfi and O. umbonatus.

The mid- to late Miocene marks one of the last warm periods of the Neogene, before the descent in to the ice house climate of the late Pliocene and Pleistocene. The mid- to late Miocene climate was long overlooked, but receives increasingly more interest. This study used organic geochemical biomarker distributions and their isotopic signatures in sediment samples from the Japan Sea, recovered during IODP Expedition 346 and ODP Leg 127/128. It was the aim to reconstruct paleoceanographic and paleoclimatic changes over the last 18 Ma. Reconstructed sea surface temperatures revealed declining temperatures since the Mid-Miocene Climatic Optimum, possibly driven by a long-term decline in atmospheric CO2. Reconstructed pCO2 using alkenone paleobarometry, revealed a late Miocene decline from circa 520 μatm to 380 μatm. A decline in this range is required to trigger the onset of the late Miocene C4 plant expansion, which was also fully detected in the sedimentary record from the Japan Sea. Stable isotope analysis of n-alkanes (δD and δ13C) revealed an intensified summer monsoon from 5-3 Ma, which also led to a freshening of surface waters in the Japan Sea. Overall, the Japan Sea is a suitable study area for the late Miocene climate change.

Climate change predictions indicate an increase in the frequency and duration of flood events along with longer dry antecedent conditions , which could alter patterns of trace metal release from contaminated river bank sediments. This study took a laboratory mesocosm approach. Chemical analysis of water and sediment samples allowed the patterns of Pb and Zn release and key mechanisms controlling Pb and Zn mobility to be determined. Trace metal contaminants Pb and Zn were released throughout flooded periods, however the highest concentrations of dissolved Pb were observed at the end of the longest flood period and high concentrations of dissolved Zn were released at the start of a flood. These concentrations were found to exceeded environmental quality standards. Key mechanisms controlling mobility were (i) anglesite solubility control of dissolved Pb, (iii) evaporation, precipitation and dissolution of Zn sulphate salts, (iii) oxidation of galena and sphalerite, (iv) reductive dissolution Mn/ Fe hydroxides and co precipitation/adsorption with Zn. In light of climate change predictions these results indicate future scenarios may include larger or more frequent transient 'pulses' of dissolved Pb and Zn released to river systems. These short lived pollution episodes could act as a significant barrier to achieving the EU Water Framework Directive objectives.

We consider a simple semi-empirical scoping calculation in conjunction with mathematical models to estimate the radius of impact (Ri) and to determine the circumstances under which gold mines in Ghana are likely to have adverse effect on water levels and volumes in surrounding villages/farms. The approach involves the assessment of local mine geometries, collation and examination of hydraulic conductivity data and the assessment of recharge infiltration rate. Most of the models used with the entire conductivity dataset (Group A) predicted very close radius of impacts to mine with less than few 100m with a median distance of 400m from the mine’s edge. Although it is expected that 25% of cases could reach up to 2km and further if the system was anisotropic. Derogation of water level and volume is more of a problem for Group B and C aquifer systems of higher conductivity values. Model results show that 50% of cases could reach up to 3.6km with a range of 2.7km to 5.1km, and 3km with a range of 2km to 4.6km from mine centre respectively. Nevertheless, Ri could reach 7.6km and further in extreme cases if the system was anisotropic. With regards to Ghana, by constraining conductivity values using water volumes produced by mines in Ghana, and comparing with the model output, it is tentatively suggested that the most likely Ri values are those calculated with the Group B dataset. It should, however, be noted that this results are very sensitive to hydraulic conductivity, and therefore there is the need in Ghana to publish conductivity and volume data to enable suggestions from this work to be confirmed.

A methodology of assessment is presented of the groundwater resources available in fracture zones, within the weathered mantle of gneiss, migmatite and granite. A model of weathering is developed, and values of porosity, hydraulic conductivity and electrical resistivity assigned to the different grades of weathering. A geophysical technique is developed, based upon a combination of electrical resistivity profiling and sounding, which allows a volume estimate of the various weathering grades to be made. A finite difference algorithm is used for this estimate which enables the apparent resistivity response of an inhomogeneous resistivity distribution to be calculated. An iterative approach is then adopted, adjusting the resistivity model until the calculated response agrees with the field data. An analysis of recharge in a savanna climate is developed based upon the Monteith equation for predicting evapotranspiration, and upon a model of unsaturated zone soil moisture movement. The recharge function developed is included in a one dimensional catchment water balance model. The results from this model are compared with observed runoff and groundwater hydrographs. The estimate of recharge is combined with the estimate of aquifer storage to produce an assessment of available groundwater. Optimal methods for the development of the resource are discussed. While developed in Northern Nigeria, the methodology of assessment is applicable to any similar geological and climatological environment.

Spaceborne Synthetic Aperture Radar (SAR) sensors obtain regular and frequent radar images from which ground motion can be precisely detected using a variety of different techniques. The ability to remotely measure slope displacements over large regions has many uses and advantages, although the limitations of an increasingly common technique, Differential SAR Interferometry (D-InSAR), must be considered to avoid the misinterpretation of results. Areas of low coherence and the geometrical effects of mountainous terrain in SAR imagery are known to hinder the exploitation of D-InSAR results. A further major limitation for landslide studies is the assumption that variable rates of movement over a given distance cannot exceed a threshold value, dependent upon the SAR image pixel spacing, the radar sensor wavelength and satellite revisit frequency. This study evaluates the use of three SAR image modes from TerraSAR-X and ENVISAT satellites for monitoring slow-moving landslides in the densely vegetated Three Gorges region, China. Low coherence and episodically fast movements are shown to exceed the measureable limit for regular D-InSAR analysis even for the highest resolution, 11-day interferograms. Subsequently, sub-pixel offset time-series techniques applied to corner reflectors and natural targets are developed as a robust method of resolving time-variable displacements. Verifiable offsets are generated with the TerraSAR-X imagery and the precise movement history of landslides is obtained over a period of up to four years. The capability to derive two-dimensional movements from sub-pixel offsets is used to infer a rotational failure mechanism for the most active landslide detected, and a greater understanding of the landslide behaviour is achieved through comparisons with likely triggering factors and 2D limit equilibrium slope stability analysis.

Northern Ireland Waterloo Mudstone Formation has received relatively little attention due to the scarcity of exposures and poor availability of subsurface records. The recent recovery of latest Triassic to Early Jurassic strata from boreholes permits further study of biostratigraphical and palaeoenvironmental using foraminifera and ostracods. The samples are from boreholes (Ballinlea-1, Magilligan and Carnduff-1) and exposures (White Park Bay, Tircrevan Burn, Larne, Ballygalley, Ballintoy and Kinbane Head). The age of the sections, established using foraminiferal biozonation ranges from latest Triassic (Rhaetian) to earliest Pliensbachian (JF9a). The assemblages recovered broadly similar to those elsewhere in NW Europe; European Boreal Atlantic Realm. The latest Rhaetian to earliest Sinemurian low diverse microfossil assemblages dominant by metacopid ostracods with occasional influx of opportunist foraminifera but gradually, foraminiferal abundances exceed the ostracods in the Early Sinemurian onwards with their highest diversity in the Late Sinemurian. The foraminiferal assemblages are dominated by foraminifera of the Lagenida, other groups include the Miliolida, Buliminida and Robertinida. Based on the microfossils, the sediments are considered to represent confined inner shelf environment in latest Rhaetian to Hettangian then gradually recovered to well-oxgenated, open marine deposits of outermost inner shelf to middle shelf in Early Sinemurian to Early Pliensbachian.

Highly ordered, stable and reproducible TIO\(_2\) NMs were synthesized using different precursors and alcohol mixtures. Various shapes of TIO\(_2\) including spherical NPs with shape factor of 0.9 or more, nanocubes, nanorods and ellipsoids were successfully fabricated. Spherical round anatase and rutile ellipsoids were selected and stabilized with different surfactants including PEG, PVP, sodium citrate and SRFA. Sodium citrate and SRFA proved to be the best stabilizing agents as compared to other surfactants used. The stabilized NMs were tested for their aggression kinetics in the presence of mono and divalent electrolytes (NaNO\(_3\), NaCl, CaN\(_2\)O\(_6\), CaCl\(_2\)). The aggregation kinetic studies showed that rutile ellipsoids behaved well against different mono and divalent cations. The CCC's observed for sodium citrate stabilized NMs were significantly higher than SRFA stabilized NMs, showing that sodium citrate is a better stabilizing agent than SRFA. The SRFA and sodium citrate stabilized NMs were studied for porous media column transport. The mobility of the rutile ellipsoids was greater than spherical anatase. Bare anatase NPs gave no breakthrough and the NPs clogged both the sandstone and glass bead columns; while bare rutile ellipsoids gave nearly 100% breakthrough curves. Only 40% or less NPs were released from sandstone columns. More release of NPs with SRFA flush is also important as it reflects the ultimate fate and behaviour of TiO\(_2\) NPs in natural environment which is rich in humic substances.

Reactive groundwater contaminant transport is dependent upon hydraulic and geochemical property distributions. The aim of this research was to determine, for an example fluvial sandstone: (i) the degree of correlation between geochemical property values and lithofacies (LFs); and (ii) the effect of the correlations on reactive solute transport. A 60 m core from the carbonate-cemented, red-bed Triassic Sherwood Sandstone Group was examined. Five fluvial LFs were identified, in fining upwards cycles from a channel lag sandstone (LF5) to a low energy mudstone (LF1). The main geochemical properties investigated were carbonate content, oxide content, sorption capacity, cation exchange capacity (CEC) and selectivity coefficient; Surface area and colour were also studied. There is a clear distinction in carbonate content, CEC, selectivity coefficient and Fe and Mn oxide content between LF1 and LF2, the ‘mud’ LFs, and the matrix of LF3, LF4 and LF5, the ‘sand’ LFs. In addition, the pellets change the bulk geochemical properties of the sand LF units. Modelling indicated that the pellets can affect solute mobility significantly. Selectivity coefficients show a possible depth zoning. Distribution parameter values obtained characterize the sequence for geochemical modelling and uncertainty estimation. Oxide coating thickness was estimated at about 100nm. CEC was found to be well-correlated with surface area. Colour/Fe/Mn content correlations suggest a possibility in future to use colour logging to indicate oxide content and possibly even surface area and CEC. As the sequence examined appears typical of many red-bed fluvial sequences, it is suggested that the findings may also be typical of other similar continental sandstones.

The Antarctic Peninsula (AP) has been one of the most rapidly warming regions on this planet. This warming has been accompanied by major glaciological changes such as tidewater glacier retreat, ice-shelf retreat and collapse alongside acceleration of outlet glaciers in response to ice-shelf removal. As faster owing glaciers deliver more ice from the ice sheet's interior to the margins, the AP has been identified as an important contributor to global sea-level rise (SLR). However, comprehensible SLR projections of the AP induced by ice dynamics over the next three centuries are still lacking. In this thesis, numerical ice-sheet models are utilised to present scenario-based ice dynamic SLR projections for the AP.