Upland environments are important sources of mercury (Hg) to downstream wetlands and water bodies. Hydrology is instrumental in facilitating Hg transport within, and export from watersheds. Two complementary studies were conducted to assess the role hydrological processes play in controlling Hg mobility and transport in forested uplands. A field study compared runoff and Hg fluxes from three, replicate hillslope plots during two contrasting spring snowmelt periods, in terms of snowpack depth and timing. Hillslope Hg fluxes were predominately flow-driven. The melting of soil frost significantly delayed a large portion of the Hg flux later into the spring following a winter with minimal snow accumulation. A microcosm laboratory study using a stable Hg isotope tracer applied to intact soil cores investigated the relative controls of soil moisture and precipitation on Hg mobility. Both hydrologic factors control the mobility of contemporary Hg; with greatest Hg flushing from dry soils under high-flow conditions.

Since their introduction to Lake Erie, dreissenid mussels may have reengineered the cycling of nutrients in the lake so that the nearshore benthic community intercepts, retains, and recycles greater quantities of nutrients. This study traces particulate matter on a basin scale by characterizing the chemical composition (POC and PN concentrations, POC/PN mass ratios, δ¹³C and δ¹⁵N) of suspended particulate matter in Lake Erie, three tributary inflows, and the lake outflow between May and October, 2002. The data are used to 1) determine the relative contributions of allochthonous and autochthonous sources to suspended particulate matter, 2) identify possible sources of suspended particulate matter, and 3) compare suspended particulate matter in the eastern basin of Lake Erie with that in the central and western basins. Mean POC concentrations range from 175 to 4494 ??g/L and mean PN concentrations range from 33 to 812 ??g/L in this system. Mean POC/PN mass ratios are similar across all sampling locations, ranging between 4. 5 and 6. 9, and indicate that suspended particulate matter at these sites is mainly derived from autochthonous sources, particularly plankton. The ranges of δ¹³C (-34 to -22 ?) and δ¹⁵N (1 to 12 ?) identify terrestrial plants and soil matter, aquatic macrophytes, phytoplankton, and sewage as possible sources of suspended particulate matter at all sites. Plankton is probably the dominant source of suspended particulate matter at each site, with smaller contributions from allochthonous and other autochthonous sources. Significant differences in the concentration and isotope data between inflow and lake or outflow sites indicate that tributary inflows may receive greater contributions from terrestrial plants and soils and aquatic macrophytes than the lake and outflow. δ¹⁵N signatures also identify animal manure as a possible source of suspended particulate matter at the inflows. PN concentrations and δ¹⁵N signatures suggest that the shallowest nearshore sites close to Peacock Point in the eastern basin receive PN from a source that is not present at the other eastern basin sites or at the sites in the central and western basins. This source may be related to dreissenid mussels at these nearshore sites recycling nitrogen back into the water column.

This thesis presents the results of contemporary limnological and palaeolimnological investigations of a series of crater lakes in order to reconstruct the palaeoenvironmental history of western Uganda, East Africa. The research examines questions of spatial and temporal heterogeneity of climate changes in the context of growing human impacts on the landscape over the last millennium. Sediment records from two lakes, Nyamogusingiri and Kyasanduka within the Queen Elizabeth National Park (QENP) were investigated to look at the long term records of climate and environmental change (spanning the last c. 1000 years). Five shorter cores across a land-use gradient were retrieved to assess the impact of human activity on the palaeoenvironmental record over the last ~150 years. High-resolution (sub-decadal), multiproxy analyses of lake sediment cores based on diatoms, bulk geochemistry (C/N and δ13C) and sedimentary variables (loss-on-ignition, magnetic properties and physical properties) provide independent lines of evidence that allow the reconstruction of past climate and environmental changes. This multiproxy approach provides a powerful means to reconstruct past environments, whilst the multi-lake approach assists in the identification and separation of local (e.g. catchment-scale modifications and groundwater influences) and regional effects (e.g. climatic changes). The results of a modern limnological survey of 24 lakes were used in conjunction with diatom surface sediment samples (and corresponding water chemistry) from 64 lakes across a natural conductivity gradient in western Uganda (reflecting a regional climatic gradient of effective moisture) to explore factors controlling diatom distribution. The relationships between water chemistry and diatom distributions were explored using canonical correspondence analysis (CCA) and partial CCA. Variance partitioning indicated that conductivity accounted for a significant and independent portion of this variation. A transfer function was developed for conductivity (r2jack = 0.74). Prediction errors, estimated using jack-knifing, are low for the conductivity model (0.256 log units). The final model was applied to the core sediment data.This study highlights the potential for diatom-based quantitative palaeoenvironmental reconstructions from the crater lakes in western Uganda. Sedimentary archives from the Ugandan crater lakes can provide high-resolution, annual to sub-decadal records of environmental change. Whilst all of the lakes studied here demonstrate an individualistic response to external (e.g. climatic) drivers, the broad patterns observed in Uganda and across East Africa suggest that the crater lakes are indeed sensitive to climatic perturbations such as a dry Mediaeval Warm Period (MWP; AD 1000-1200) and a relatively drier climate during the main phase of the Little Ice Age (LIA; c. AD 1500-1800); though lake levels in western Uganda do fluctuate, with a high stand c. AD 1575-1600). The general trends support the hypothesis of an east to west (wet to dry) gradient across East Africa during the LIA, however, the relationship breaks down and is more complex towards the end of the LIA (c. AD 1700-1750) when the inferred changes in lake levels at Nyamogusingiri and Kyasanduka are synchronous with changes observed at Lakes Naivasha (Kenya) and Victoria and diverge from local lake level records (from Edward, Kasenda and Wandakara). Significant changes in the lake ecosystems have occurred over the last 50-75 years, with major shifts in diatom assemblages to benthic-dominated systems and an inferred increase in nutrient levels. These changes are coincident with large sediment influx to the lakes, perhaps as a result of increasing human activity within many of the lake catchments.

Dispersal is a fundamental process that shapes many aspects of population ecology and evolution. Dramatic local population declines brought about by anthropogenic-driven changes to ecological processes are unfortunately becoming ubiquitous and increasing the urgency to understand dispersal behaviour in many species. For species where direct methods of tracking movement and dispersal are unsuitable, other indirect methods need to be employed to understand and characterise these behaviours. The steep population decline, due to predation, at the largest EU population of Leach’s storm-petrels Oceanodroma leucorhoa (St Kilda, Scotland), and the potential part immigrant birds have in buffering this threat, highlighted the need to understand dispersal and connectivity of widely spaced colonies in this species. The implications for the persistence of local colonies and the wider population of Leach’s storm-petrels could then be assessed. A population genetic analysis of 9 colonies across the North Pacific and Atlantic distribution, using two DNA markers (mtDNA control region and microsatellites), revealed ocean basin differentiation (Global ST = 0.32 P <0.0001, Global FST = 0.04, P <0.0001) but also identified a migrant individual in the Pacific population (STRUCTURE migrant assignment). The Atlantic population was found to be genetically homogenous, with patterns of historical and contemporary gene flow, indicating that long-distance effective dispersal is prevalent in Leach’s storm-petrels within the ocean basin. Bayesian stable isotope analysis of carbon and nitrogen (13C & 15N) provides evidence for natal dispersal as an important dispersal mechanism, and reveals movement of immature birds between colonies during the breeding season as a likely mechanism to promote inter-colony exchange and gene flow. Stable isotope comparison also identified mixing on wintering grounds as another possible influence on dispersal. The potential for immigrant birds to offset the loss caused by predation at the St Kilda colony is supported by these studies, and will likely help the persistence of the colony in the short-term. However, future viability is debateable considering the evidence for both avian and mammalian predation. This research provides a better understanding of the extent and mechanism of dispersal in the Leach’s storm-petrel, which is important to predict the potential impact of environmental change and, where possible, implement effective population management for this species.

The brown trout, Salmo trutta L., displays one of the most variable and polymorphic life-history strategies of all the salmonids. In some populations, individuals spend their whole life-cycle in the river (freshwater-resident) whereas in others, a varying proportion migrates to sea for variable amounts of time to better feeding conditions before returning to spawn (anadromous). The ‘decision’ if an individual will migrate or not will be determined by the balance of the costs and benefits of following a particular life-history strategy. The balance of these, which do not affect males and females equally, will determine the future success (measured by fitness) of each strategy. This research addresses the influences of parental contribution, mainly maternal effect, of anadromous and freshwater-resident brown trout on offspring performance and subsequent life-history. A partial migratory population of brown trout was studied in the Tadnoll Brook, one of the seven major tributaries on the River Frome. The tributary is classified as a circum-neutral chalk stream, 9.9 km long with a catchment approximately 50 km2. Carbon and nitrogen stable isotope analysis (SIA) was used to quantify maternal reproductive contribution of anadromous and freshwater-resident brown trout to offspring and determine the future success (measured by fitness) in terms of size and time of emergence. A panel of 12 microsatellite loci was used to assign parentage to 0+ parr. Using field data collected over 1.5 years on individual fish, this study tested parental influence on offspring performance in terms of size and growth rate and calculate the reproductive contribution of maternal/paternal anadromous and freshwater-residents. Adult life-history strategy was identified using a combination of results from SIA, PIT tag data and ecological data (body size, temperature). Parr life-history strategy (1+) was inferred using PIT tag detection data. The results of the SIA indicated fry of anadromous females emerged earlier and at a larger size than fry of freshwater-resident females. Parentage assignment of parr was low (28 %), with 8 parr assigned to both parents and 43 assigned to only a single parent. There was no detectable effect of parental life-history on parr size and growth rate, however the raw data may suggest offspring of anadromous parents have an early size advantage but a slower growth compared to offspring of freshwater-resident parents during the first year of the parr stage. Twenty-four percent of the offspring were identified as putative smolts at 2+ and both forms interbred and could produce offspring of each life-history. Estimates of reproductive contribution (SIA and growth) show a higher proportion of anadromous females and males (growth only) contributed to offspring production. The results of this research indicate that the maternal anadromous contribution is higher in the Tadnoll Brook population, affording fitness benefits to their offspring during early ontogeny such as size advantages and emerging at a more profitable time to establish feeding territories. Adult life-history does not appear to influence juvenile (0+ parr) life-history but may have an effect on offspring performance. The presence of both forms in the population suggests the anadromous fitness benefits to offspring may only have an affect during ontogeny and early stages of growth. Then after juveniles reach a size threshold environmental factors influence offspring life-history, resulting in the largest parr with the fastest growth adopting an anadromous life-history.

The present thesis deals with the related themes of mortality and growth in coral reef fishes. In the first chapter, a nine-year dataset from Bermuda is used to quantify how reef fish populations respond to the introduction of a trap-fishing ban, finding that herbivores exhibit extremely strong recovery, but that stock-recruitment relationships may be decoupled by a numerical response in a meso-predator. In the second chapter, a dataset from Bonaire is used to test the efficacy of the widely-used coefficient of natural mortality, M, in modelling a population of stoplight parrotfish (Sparisoma viride). As determined from simulation models, this statistical coefficient performs considerably less well than a novel mechanistic function that partitions mortality into size- and age-based processes and achieves extremely good fits to the field data. The third chapter presents a new approach to estimating growth parameters of reef fish from tagging data that exploits the disproportionate response of certain parameters to misestimates in the true age of the tagged individuals. The method works considerably better than the most widely used method when sample sizes are small, as is commonly the case in reef fish tagging studies where recapture rates tend to be low. The fourth and final chapter uses non-lethal stable isotope techniques to tease apart the invasion dynamics of Indo Pacific lionfish (Pterois spp.) that are currently colonising the wider Caribbean. The results show that lionfish exhibit habitat-specific ontogenetic shifts in prey selection, inflicting elevated mortality on small, bommie-dwelling fishes on forereefs but switching to seagrass-foraging invertivores as they grow. Lionfish also display ontogenetically shifting competition with native Nassau grouper (Epinephelus striatus), which may provide a greater barrier to invasion success on patch reefs than on fore reefs, where competitive overlap is diminished. The thesis concludes with a discussion of some lines of enquiry that could not be undertaken owing to time or data limitations, but which may hold as much interest for the reader as they do for the author.

Resonant ionization laser ion sources are applied worldwide to increase purity and intensity of rare isotopes at radioactive ion beam facilities. Especially for heavy elements the laser wavelengths required for efficient resonant laser ionization are not only element dependent, but also vary to small degrees from isotope to isotope. Since the first operation of an actinide target at ISAC-TRIUMF in 2008, the demand for neutron-rich isotopes far away from stability has steadily increased. Those isotopes often have very low production rates so that often only a few ions per second are released. In order to study isotope shifts and hyperfine structure of silver, actinium and astatine, in-source resonant ionization spectroscopy in combination with radioactive decay detection has been applied. Despite the Doppler limited resolution, it has the advantage that it is ultra-sensitive and the atomic spectrum for the nuclear ground and isomeric states can be investigated individually. An isobaric separation has been demonstrated for 115-119Ag, where the hyperfine structure of one state showed a splitting of 22 GHz to 38 GHz while for the other state only a single peak spectrum can be resolved. For astatine and actinium, the main interest is to measure and study the optical isotope shift, which is for the first excitation step for neutron-rich isotopes in the order of IS_FES≈±3.7GHz/u for both elements, as these observables give insight into nuclear moments and shape. In addition, also the isotope shift of the second excitation step for astatine has been measured to IS_SES,At≈-1.7GHz/u. Laser spectroscopy on astatine has mainly been performed on the neutron-deficient isotopes 199,205At due to high count rates and low isobaric contamination. With the results obtained it is possible to extrapolate the required wavelength for ionizing and delivering the isotopes 221-225At which are of interest to e.g. electric dipole moment studies. / October 2017

Stable isotope analysis (SIA) is a valuable tool in ecotoxicology because δ13C and δ15N may provide insights into the trophic transfer of contaminants in a food web. The relationship between a species’ trophic position (TP, determined from δ15N) and internal concentration of biomagnifying contaminants can be established and used for regulatory purposes. However, the exposure of organisms to xenobiotics incurs physiological costs, and the stable isotope signature of a consumer reflects not only diet but also a physiological state. The latter raises questions regarding the interpretation of stable isotope signatures in contaminated areas. Therefore, the aim of this Thesis was to evaluate the behaviour of consumers’ stable isotope signatures in stressed systems, with a primary focus on the effects of environmental contaminants. In paper I, the physiological costs of chemical exposure were found to alter incorporation rates of dietary nitrogen and carbon in a consumer by influencing both growth and metabolic turnover, with resulting changes in isotope signatures relative to a control system. In paper II, the diet-consumer discrimination factors for 15N and 13C were confirmed to increase under chemical exposure mediated via increased metabolic costs. However, the physiological response was low and translated into only minor shifts in the δ13C and δ15N. The predictability of exposure effects on the stable isotope signature was demonstrated in paper III, in which animals exposed to a chemical with a known mode of action presented expected effects on elemental composition, body size, biomarkers of oxidative stress and the stable isotope signatures. Moreover, consumers’ oxidative balance was found to be related to their δ15N values, thus providing evidence of the kinetic isotope effect on the oxidative status. However, despite the alterations in stable isotope signatures observed in laboratory settings (papers I-III), the effect of xenobiotics on the TP estimates was nil or minor in the field-collected animals. Moreover, the TP values were not significantly different between the animals in the contaminated and the reference habitats because of the high overall uncertainties in the TP estimates (paper IV). Also, the TP estimates based on δ15N in bulk material were more similar between the contaminated and the reference systems than TP estimates based on δ15N values in amino acids. Therefore, the latter method appears more sensitive towards xenobiotics (and, possibly, other environmental stressors) and thus less suitable for TP assessment in contaminated areas. This Thesis improved the overall understanding of the applicability of SIA in stressed systems by establishing relationships between various exposure regimes, physiological responses and the stable isotope signatures in consumers. In model species at low trophic levels, the exposure to xenobiotics was found to significantly affect δ13C and δ15N values, which can be expected whenever physiological responses are detected. However, because of the overall high uncertainty in TP estimates, no significant differences between contaminated and control systems were detected, although the estimated TP were consistently higher in the contaminated systems. Future research should focus on higher trophic levels, in which effects of a greater magnitude can be expected. Moreover, the effects in entire food webs should be addressed rather than single prey–consumer relationships as well as other environmental variables that may contribute to the stable isotope variability in and among systems under various environmental pressures. / <p>At the time of the doctoral defense, the following papers were unpublished and had a status as follows: Paper 3: Manuscript. Paper 4: Manuscript.</p>

In an exploratory study, techniques were developed for isolating bulk plant proteins and measuring the ¹³C isotopic compositions of their constituent amino acids by HPLC-IRMS. Samples of plants expected to be of potential palaeodietary significance in northwestern Europe were selected for investigation. Different tissues of plants, leaves and seeds, may be distinguished from each other by the relative ¹³C isotopic compositions (‘isotopic signatures’) of the amino acids of their constituent proteins. For each tissue type, different plant types may be distinguished in the same way. These signatures can vary slightly according to environment and season, but the variation among types is greater than this. For leaves, isotopic signatures can be used to differentiate (i) nettles, (ii) true grasses, (iii) reeds etc, (iv) trees, (v) legumes, (vi) maize, (vii) freshwater plants and (viii) marine algae. For seeds, these signatures are able to differentiate (i) wheat-type cereals, (ii) barley-type cereals, (iii) C4 cereals, (iv) pseudocereals, (v) legumes and (vi) tree nuts. From investigations using a mixing model, it appears that these signals, particularly those of essential amino acids, are reflected in the tissues of their consumers. Freshwater plants are identified as the base of the food chain for dragonfly larvae, marine algae as the diet of marine molluscs and grass as the diet of archaeological cattle and aurochs. Isotopic ‘marine signals’ identified by previous researchers have been refined using these data and the isotopic signatures of fish muscle. These findings are expected to be of particular value in the study of palaeodiets using proteins from archaeological tissues, especially bone and hair. This approach will also find application in the fields of plant physiology and biochemistry.

This thesis presents the development of a dual-isotope simulation in a hydrological model, and its application to the lower Nelson River basin. The purpose of this study is to find if the simulation of stable water isotopes aids in hydrological simulation, and if a dual-isotope simulation is an improvement over a single-isotope simulation. The isoWATFLOOD model was enhanced to include δ2H and improve physical representativeness. The model was calibrated using various isotope and flow simulation error functions. Internal hydrologic storages and fluxes were verified by comparing simulated isotope values to observed isotope data. Adding isotope error to the calibration resulted in small but consistent improvements to the physical basis of calibrated parameter values. Isotope simulation error was found to be the best predictor of streamflow simulation performance beyond the calibration period. The dual-isotope simulation identified a number of model limitations and potential improvements from the verification of internal hydrologic storages. / October 2016