Chamber investigations of atmospheric mercury oxidation chemistry

Mercury is a potent neurotoxin even at low concentrations. The unoxidised metal has a high vapour pressure and can circulate through the atmosphere, but when oxidised can deposit and be accumulated through the food chain. This work aims to investigate the oxidation processes of atmospheric Hg0(g). The first part describes efforts to make a portable Hg sensor based on Cavity Enhanced Absorption Spectroscopy (CEAS). The detection limit achieved was 66 ngm−3 for a 10 second averaging time. The second part of this work describes experiments carried out in a temperature controlled atmospheric simulation chamber in the Desert Research Institute, Reno, Nevada, USA. The chamber was built around an existing Hg CRDS system that could measure Hg concentrations in the chamber of<100 ngm−3 at 1 Hz enabling reactions to be followed. The main oxidant studied was bromine, which was quantified with a LED based CEAS system across the chamber. Hg oxidation in the chamber was found to be mostly too slow for current models to explain. A seven reaction model was developed and tested to find which parameters were capable of explaining the deviation. The model was overdetermined and no unique solution could be found. The most likely possibility was that the first oxidation step Hg + Br →HgBr was slower than the preferred literature value by a factor of two. However, if the more uncertain data at low [Br2] was included then the only parameter that could explain the experiments was a fast, temperature independent dissociation of HgBr some hundreds of times faster than predicted thermolysis or photolysis rates. Overall this work concluded that to quantitatively understand the reaction of Hg with Br2, the intermediates HgBr and Br must be measured. This conclusion will help to guide the planning of future studies of atmospheric Hg chemistry.

Plasmonic gold nanostructures: optical properties and application in mercury detection

This thesis investigates the application of plasmonic gold nanostructures for mercury detection. Various gold and silver single nanostructures and gold nanostructure assemblies were characterised in detail by correlated single nanostructure spectroscopy and electron microscopy. Several routes for mercury detection were explored: plasmon resonance energy transfer (PRET) upon Hg2+ binding to immobilised gold nanoparticle-organic ligand hybrid structures and amalgamation of single immobilised gold nanorods upon chemical and upon electrochemical reduction of Hg2+ ions. The amalgamation approach showed large potential with extraordinary shifts of the nanorods’ scattering spectra upon exposure to reduced mercury; a result of compositional and morphological change induced in the nanorod by amalgamation with mercury. A shift of 5 nm could be recorded for a concentration as low 10 nM Hg2+. Through detailed time-dependent experiments insights into the amalgamation mechanism were gained and a model comprising 5 steps was developed. Finally, spectroelectrochemistry proved to be an excellent way to study in real time in-situ the amalgamation of mercury with gold nanorods paving the way for future work in this field.

The ecology of the song thrush, Turdus philomelos Br., in Ireland

Over the last 30 years, western European Song Thrush populations have declined with the steepest decline recorded on British farmland. Changes in agricultural practices have been implicated in these population declines. Ireland is an agriculturally dominated landscape but changes in agriculture here have occurred on a relatively slower rate and scale. Little is known about the ecology of the Song Thrush in Ireland, even though it is not classified as a species of conservation concern here. Some decline is thought to have occurred but the current breeding population appears to be stable and widespread. In light of these facts, this study investigated various aspects of Song Thrush ecology in relation to the Irish landscape from 2001-2003. The breeding season extended from mid March to late June, where mean clutch size was 4.1 and number of fledglings was 3.7. There were very few third broods. Daily nest survival rates were calculated for egg stage 0.9362, incubation stage 0.9505 and nestling stage 0.6909. Most nest failures were due to avian predation at both egg and chick stages. Most nests were located 1.3 -2.4m from the ground at trees, bushes or hedgerow. Clutch size was significantly higher on farmland than garden & parkland and woodland, and the number of fledglings was significantly lower in nests in trees than hedgerow and bush sites. Daily nest fail rates were significantly higher at tree sites and partly concealed nests. Nesting areas had significantly denser vertical vegetation than non-nesting areas. Mercury and the organochlorine HEOD were the most common contaminants in Song Thrush eggs and livers. However concentrations and occurrence were low and of no apparent biological or ecological concern. The presence of breeding Song Thrushes was influenced by mixed surrounding farmland, the absence of grass surrounding farmland, ditches especially wet ones, tall dense vegetation and trimmed boundaries. Song Thrush winter densities were predicted by ditches, with wet or dry, low thin vegetation and untrimmed boundaries. Winter densities were almost double that of the breeding season, probably due to the arrival and passage of migrating Song Thrushes through the country, especially in November. Changes in Irish agriculture did not differ significantly in areas of Song Thrush breeding population stability and apparent decline during 1970 1990. Even though the current breeding population heavily uses farmland, woodland, human and scrub habitats are more preferred. Nevertheless no farmland habitat was avoided, highlighting a positive relationship between breeding Song Thrushes and Irish agriculture. This appears to be in contrast with findings between breeding Song Thrushes and British agriculture. Theses findings are compared with other studies and possible influences by agricultural intensification, climate, latitude and insular syndrome are discussed. Implications for conservation measures are considered, especially for areas of decline. Even though Song Thrushes are currently widespread and stable here, future environmental consequences of longer-term changes in Irish agriculture and perhaps climate change remain to be seen.

WIMU instrumentation of assassin trainer & skeleton sled

Skeleton is a high‐speed Winter Olympic sport performed on the same twisting, downhill ice tracks used for Bobsleigh & Luge. The single rider sprints and pushes their sled for 20‐30m on a level start section before loading and going through a twisting course of over 1km, at speeds up to 140km/h, experiencing up to 5g. In competition, the top athletes can be within a fraction of a second of each other. The initial short pushing period is believed to be critical to overall performance but it is not well understood. A collaborative project between University of Bath, UK Sport and Tyndall National Institute is instrumenting skeleton athletes, training equipment and test tracks with Tyndall’s Wireless Inertial Measurement Unit technology in order to investigate and improve understanding of this phase of a skeleton run. It is hoped this will lead to improved training regimes and better performance of such elite, Olympic level athletes. This work presents an initial look at the system as implemented and data recorded.

Initial losses, corporate governance and earnings management

This thesis examines the relationship between initial loss events and the corporate governance and earnings management behaviour of these firms. This is done using four years of corporate governance information spanning the report of an initial loss for companies listed on the UK Stock Exchange. An industry- and sizematched control sample is used in a difference-in-difference analysis to isolate the impact of the initial loss event during the period. It is reported that, in general, an initial loss motivates an improvement in corporate governance in those loss firms where a relative weakness existed prior to the loss and that these changes mainly occur before the initial loss is announced. Firms with stronger (i.e. better quality) corporate governance have less need to alter it in response to the loss. It is also reported that initial loss firms use positive abnormal accruals in the year before the loss in an attempt to defer/avoid the loss — the weaker corporate governance the more likely is it that loss firms manage earnings in this manner. Abnormal accruals are also found to be predictive of an initial loss and when used as a conditioning variable, the quality of corporate governance is an important mitigating factor in this regard. Once the loss is reported, loss firms unwind these abnormal accruals although no evidence of big-bath behaviour is found. The extent to which these abnormal accruals are subsequently unwound are also found to be a function of both the quality of corporate governance as well as the severity of the initial loss.