Sectoral impacts on the diversity of carabid beetles (Coleoptera: Carabidae) and their associated ecosystem service of biocontrol

This thesis aimed to provide an understanding of how human-induced changes in the economic sectors of agriculture and transport affect carabid diversity, potential carabidmediated biocontrol and predator-pest interactions. The research involved both observational and manipulative laboratory and field-based studies. Observational research consisted of two large-scale investigations of (1) the impact of Miscanthus and oilseed rape production (n=45) and (2) the impact of horticultural and ecological based landscaping of roadside verges (n=64). This research is the first record of carabid diversity, potential biocontrol and community assemblage with respect to bioenergy crop production and roadside landscaping in an Irish context and it is also an important addition to the limited knowledge of carabid populations in these ecosystems internationally. Manipulative work involved the examination of the role predator identity, diversity and biomass play in the suppression of pollen beetle larvae (an economically damaging insect pest of oilseed rape in Europe), using a novel experimental design called ‘simplex’. To complement this research, an additional field study on the impact of low and high oilseed rape pesticide management on carabid species richness and abundance, and crop yield, was also conducted. This research is a great contribution to the existing understanding of what constitutes the important components of predator biodiversity and expands the knowledge of the usefulness of carabid predators in the context of pollen beetle larvae control. In particular, the work shows that the abundance or biomass of beetles has an effect that is far larger than the effect of diversity on the capacity of beetles to consume prey. In turn, the field study showed that pesticide applications had little impact on yield, or carabid richness, but that carabid abundance/biomass declined drastically. The work provides compelling evidence that management practices erode the useful components of biodiversity that are essential for the delivery of biocontrol services.

Optimisation of chemoenzymatic processes in asymmetric synthesis

This thesis describes the optimisation of chemoenzymatic methods in asymmetric synthesis. Modern synthetic organic chemistry has experienced an enormous growth in biocatalytic methodologies; enzymatic transformations and whole cell bioconversions have become generally accepted synthetic tools for asymmetric synthesis. Biocatalysts are exceptional catalysts, combining broad substrate scope with high regio-, enantio- and chemoselectivities enabling the resolution of organic substrates with superb efficiency and selectivity. In this study three biocatalytic applications in enantioselective synthesis were explored and perhaps the most significant outcome of this work is the excellent enantioselectivity achieved through optimisation of reaction conditions improving the synthetic utility of the biotransformations. In the first chapter a summary of literature discussing the stereochemical control of baker’s yeast (Saccharomyces Cerevisae) mediated reduction of ketones by the introduction of sulfur moieties is presented, and sets the work of Chapter 2 in context. The focus of the second chapter was the synthesis and biocatalytic resolution of (±)-trans-2-benzenesulfonyl-3-n-butylcyclopentanone. For the first time the practical limitations of this resolution have been addressed providing synthetically useful quantities of enantiopure synthons for application in the total synthesis of both enantiomers of 4-methyloctanoic acid, the aggregation pheromone of the rhinoceros beetles of the genus Oryctes. The unique aspect of this enantioselective synthesis was the overall regio- and enantioselective introduction of the methyl group to the octanoic acid chain. This work is part of an ongoing research programme in our group focussed on baker’s yeast mediated kinetic resolution of 2-keto sulfones. The third chapter describes hydrolase-catalysed kinetic resolutions leading to a series of 3-aryl alkanoic acids. Hydrolysis of the ethyl esters with a series of hydrolases was undertaken to identify biocatalysts that yield the corresponding acids in highly enantioenriched form. Contrary to literature reports where a complete disappearance of efficiency and, accordingly enantioselection, was described upon kinetic resolution of sterically demanding 3-arylalkanoic acids, the highest reported enantiopurities of these acids was achieved (up to >98% ee) in this study through optimisation of reaction conditions. Steric and electronic effects on the efficiency and enantioselectivity of the biocatalytic transformation were also explored. Furthermore, a novel approach to determine the absolute stereochemistry of the enantiopure 3-aryl alkanoic acids was investigated through combination of co-crystallisation and X-ray diffraction linked with chiral HPLC analysis. The fourth chapter was focused on the development of a biocatalytic protocol for the asymmetric Henry reaction. Efficient kinetic resolution in hydrolase-mediated transesterification of cis- and trans- β-nitrocyclohexanol derivatives was achieved. Combination of a base-catalysed intramolecular Henry reaction coupled with the hydrolase-mediated kinetic resolution with the view to selective acetylation of a single stereoisomer was investigated. While dynamic kinetic resolution in the intramolecular Henry was not achieved, significant progress in each of the individual elements was made and significantly the feasibility of this process has been demonstrated. The final chapter contains the full experimental details, including spectroscopic and analytical data of all compounds synthesised in this project, while details of chiral HPLC analysis are included in the appendix. The data for the crystal structures are contained in the attached CD.

Variability in north temperate dung beetle assemblages at different spatial and temporal scales

This study examined the spatial and temporal variability of dung beetle assemblages across a variety of scales e.g. from the between-pad scale (examining the effects of dung size and type) to larger spatial scales encompassing southern Ireland. Dung beetle assemblage structure as sampled by dung pad cohort samples and dung baited pitfall trapping were compared. Generally, the rank order of abundance of dung beetle species was significantly correlated between pitfall catches and cohort pad samples. Across different dung sizes, in both pitfall catches and cohort pad samples, the relative abundance of species was frequently significantly different, but the rank order of abundance of dung beetle was usually significantly correlated. Considerable variations in pitfall catches at temporal scales of a few days appeared to be closely related to weather conditions and rotational grazing. However, despite considerable variation in absolute abundances between consecutive days of sampling, assemblage structure typically remained very similar. The relationship between dung pad size and dung beetle colonisation was investigated. In field experiments in which pads of different sizes (0.25 L, 0.5 L, 1.0 L and 1.5 L) were artificially deposited, there was a positive relationship between pad size and both biomass and number of beetles colonising dung pads and pitfall traps. In addition, with one exception, the field experiments indicated a general positive relationship between dung pad size and biomass density (dung beetle biomass per unit dung volume). A laboratory experiment indicated that pat residence times of A. rufipes were significantly correlated with dung pad size. Investigation of naturally-deposited cow dung pads in the field also indicated that both larval numbers and densities were significantly correlated with dung pad size. These results were discussed in the context of theory related to aggregation and coexistence of species, and resource utilisation by organisms in ephemeral, patchy resources. The colonisation by dung beetles of dung types from native herbivores (sheep, horse and cow) was investigated in field experiments. There were significant differences between the dung types in the chemical parameters measured, and there were significant differences in abundances of dung beetles colonising the dung types. Sheep dung was typically the preferred dung type. Data from these field experiments, and from published literature, indicated that dung beetle species can display dung type preferences, in terms of comparisons of both absolute and relative abundances. In addition, data from laboratory experiments indicate that both Aphodius larval production and pat residence times tended to be higher in those dung types which were preferred by adult Aphodius in the colonisation experiments. Data from dung-baited pitfall trapping (from this and another study) at several sites (up to 180 km distant) and over a number of years (between 1991 and 1996) were used to investigate spatial and temporal variation in dung beetle assemblage structure and composition (Aphodius, Sphaeridium and Geotrupes) across a range of scales in southern Ireland. Species richness levels, species composition and rank order of abundances were very similar between the assemblages. The temporal variability between seasons within any year exceeded temporal variability between years. DCA ordinations indicated that there was a similar level of variability between assemblage structure from the between-field (~1km) to regional (~180 km) spatial scales, and between year (6 years) temporal scales. At the biogeographical spatial scale, analysis of data from the literature indicated that there was considerable variability at this scale, largely due to species turnover.

Biodiversity change in the Irish uplands - the effects of grazing management

As a prominent form of land use across much of upland Europe, extensive livestock grazing may hold the key to the sustainable management of these landscapes. Recent agricultural policy reform, however, has resulted in a decline in upland sheep numbers, prompting concern for the biodiversity value of these areas. This study quantifies the effects of varying levels of grazing management on plant, ground beetle and breeding bird diversity and assemblage in the uplands and lowlands of hill sheep farms in County Kerry, Ireland. Farms represent a continuum of light to heavy grazing, measured using a series of field indicators across several habitats, such as the internationally important blanket bog, home to the ground beetle, Carabus clatratus. Linear mixed effects modelling and non-metric multidimensional scaling are employed to disentangle the most influential management and environmental factors. Grazing state may be determined by the presence of Molinia caerulea or Nardus stricta, and variables such as % traditional ewes, % vegetation litter and % scrub prove valuable indicators of diversity. Measures of ecosystem functioning, e.g. plant biomass (nutrient cycling) and % vegetation cover (erosion rates) are influenced by plant diversity, which is influenced by grazing management. Levels of the ecosystem service, soil organic carbon, vary with ground beetle abundance and diversity, potentially influencing carbon sequestration and thereby climate change. The majority of species from all three taxa are found in the lowlands, with the exception of birds such as meadow pipit and skylark. The scale of measurement should be determined by the size and mobility of the species in question. The challenge is to manage these high nature value landscapes using agri-environment schemes which enhance biodiversity by maintaining structural heterogeneity across a range of scales, altitudes and habitats whilst integrating the decisions of people living and working in these marginal areas.

Invertebrate diversity in Irish and British forests

Ireland and Britain were once covered in natural forest, but extensive anthropogenic deforestation reduced forest cover to less than 1% and 5 %, respectively, by the beginning of the 20th century. Large-scale afforestation has since increased the level of forest cover to 11% in Ireland and 12% in Britain, with the majority of planted forests comprising small monoculture plantations, many of which are of non - native conifer tree species. At present the forest cover of Ireland and Britain generally consists of small areas of remnant semi-natural woodland and pockets of these plantation forests within a predominantly agricultural landscape. Invertebrates comprise a large proportion of the biodiversity found within forested habitats. In particular, spiders and carabid beetles play an important role in food webs as both predators and prey and respond to small-scale changes in habitat structure, meaning they are particularly sensitive to forest management. Hoverflies play an important role in control and pollination and have been successfully used as indicators of habitat disturbance and quality. This research addressed a number of topics pertinent to the forest types present in the contemporary Irish and British landscapes and aimed to investigate the invertebrate diversity of these forests. Spiders and carabid beetles were sampled using pitfall trapping and hoverflies were sampled using Malaise net trapping. Topics included the impacts of afforestation, the importance of open space, the choice of tree species, and the use of indicators for biodiversity assessment, as well as rare native woodlands and the effect of grazing on invertebrate diversity. The results are discussed and evidence-based recommendations are made for forest policy and management to protect and enhance invertebrate biodiversity in order to promote sustainable forest management in Ireland and Britain.