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Understanding wolf (Canis lupus) food habits provides critical information for boreal woodland caribou (Rangifer tarandus caribou; forest-dwelling ecotype) recovery strategies. By incorporating the stable isotope ratios of different caribou ecotypes into a stable isotope mixing model, I determined the relative importance of boreal woodland caribou in the summer diet of wolves in northern Manitoba, Canada. Boreal woodland caribou were primary summer prey for wolves collected in winter in registered trapline (RTL) districts where these caribou are considered rare, suggesting migratory behaviour in some wolves. Moose were primary prey in other RTL districts, followed by boreal woodland caribou, with beaver providing important contributions. Recovery strategies for woodland caribou should investigate annual wolf, caribou, and moose movement in the region to complement these findings and gain a better insight into this complex ecosystem.

ABSTRACT Collembola are known to feed on soil fungi, mycorrhizae and plant derived products. A recent study revealed that one species of Collembola, Protaphorura fimata, completely switched from decomposer to herbivore when live roots were present. The current study investigated the occurrence of diet-switching in Folsomia candida Willem. from plant detritus to live by examining its dietary preferences using stable isotope techniques. They were offering with live maize roots (C4 plant) in C3 soil, along with 15N enriched ryegrass litter and. Results demonstrated the presence of a partial diet-switch from detritus to live maize roots. Additional tests suggested that the diet-switch towards maize roots was a response to both improved food quality and greater food availability. The presence of live roots improved the body growth of F. candida and the incorporation of C from live roots into Collembola tissue suggesting

Non-statistical recrossing in ketene cycloadditions with alkenes, heavy-atom tunneling and the mechanism of the decarboxylation of Mandelylthiamin is investigated in this dissertation. A combination of experimental kinetic isotope effects and theoretical models and kinetic isotope effects is utilized for this endeavor. This dissertation also describes how the use of quasiclassical dynamic trajectories, microcanonical RRKM calculations, and canonical variational transition state theory in combination with small-curvature tunneling approximations is utilized to help advance our research methodology to better understand mechanism. In the cycloaddition of dichloroketene with cis-2-butene, significant amounts of recrossing is observed using quasiclassical dynamic trajectories. An unusual inverse 13C intramolecular KIE lead us to investigate the role that heavy atoms play in non-statistical recrossing. More importantly, this discovery has uncovered a new phenomena of entropic intermediates that not only applies to ketene cycloadditions, but can also be applicable to other "concerted" reactions such as Diels-Alder reactions. The ring-opening of cyclopropylcarbinyl radical has revealed that heavy-atom tunneling plays a major role. The intramolecular 13C kinetic isotope effects for the ring-opening of cyclopropylcarbinyl radical were unprecedentedly large and in combination with theoretical predictions and multidimensional tunneling corrections, the role of tunneling in this reaction can be better understood. The mechanism decarboxylation of mandelylthiamin has been extensively studied in the literature. However, until the use of theoretically predicted KIEs and theoretical binding motifs the rate-limiting step of this reaction has been hotly debated. In this dissertation, a discussion of how the theoretical KIEs indicate the initial C-C bond as the rate-limiting step and chelating binding motifs of pyridinium and mandelylthiamin to explain the observed catalysis is given.

Introduction The National Superconducting Cyclotron Laboratory (NSCL) is a national nuclear physics facility in which heavy ion beams are fragmented to produce exotic nuclei. In this process of fragmentation many nuclei are created, however, only one isotope is selected for experimentation. The remaining isotopes that are created go unused. The future upgrade of the NSCL to the Facility for Rare Isotope Beams (FRIB) will increase the incident energy of these heavy ion beams and amplify the current by three orders of magnitude. An aqueous beam dump will be created to collect the unused isotopes created in the process of fragmentation. Several of these isotopes are of interest for many applications including nuclear security, medical imaging, and therapy and are not currently available or are only available in very limited supply. Harvesting these isotopes from the aqueous beam dump could provide a consistent supply of these im-portant isotopes as an ancillary service to the existing experimental program. Material and Methods A liquid water target system was designed and tested to serve as a mock beam dump for exper-iments at the NSCL1. A 25 pnA 130 MeV/u 76Ge beam was fragmented using a 493 mg/cm2 thick beryllium production target. After fragmentation the beam was separated using the A1900 frag-ment separator2 set up for maximum 67Cu pro-duction using a 240 mg/cm2 aluminum wedge and a 2% momentum acceptance. The secondary beam was collected for four hours in the liquid water target system before being transferred to a collection vessel. Four additional four hour collections were made before finally shipping the five collections to Washington University and Hope College for chemical separation. Four of the five samples were separated using a two part separation scheme. First they were passed through and 3M Empore iminodiacetic acid functionalized chelation disk in a 1.25M ammonium acetate solution at pH 5. The flow through was collected and analyzed using an HPGe detector. Then 10mL of 6M HCl acid was passed through the chelation disk to remove the 2+ transition metals. The 10mL of 6M HCl acid was collected after passing through the disk and added to an anion-exchange column with 2.5 g AG1-X8 resin. The eluate was collected and then an additional 10mL of 6M HCl was passed through the column to remove the nickel. The 67Cu was then collected by passing 10mL of 0.5M HCl and the eluate was collected in 1mL fractions each analyzed by HPGe for 67Cu concentration and purity. The two highest 67Cu fractions were heated to dryness and reconstituted in 50 μL 0.1M ammonium acetate pH 5.5. 2 μL of 7.9 mg/mL NOTA-Bz-Trastuzumab was added to 45 μL of 67Cu and 3 μL 0.1M ammonium acetate pH 5.5. This solution was placed in a shaking incubator at 37 °C for twenty minutes and then analyzed by radio-instant thin layer chromatography in order to determine the per-cent of 67Cu bound to the antibody. Results and Conclusion 67Cu was collected into the liquid water target system with an average efficiency of 85 ± 5 %. The secondary beam was 73 % pure with the impurities, half-lives greater than 1 minute, listed in TABLE 1. Separation of 67Cu from the impurities resulted in an average recovery of 88 ± 3 % for a total recovery of 67Cu from the beam and separation of 75 ± 4 %. No detectable radioactive impurities were found in the final samples when analyzed using an HPGe detector. TABLE 2 shows the amount of 67Cu collected from the beam and the amount recovered decay corrected to end of bombardment. Labeling NOTA-Bz-Trastuzumab with 67Cu resulted in > 95 % radiochemical yield. Collection of the 73 % pure 67Cu beam in water and the resulting separation proved successful. These results demonstrate that radioisotopes can be collected from fragmented heavy ion beams and isolated in usable quantities and purity for many radiochemical applications. Further experimentation with an unpurified beam to better simulate conditions in the beam dump at the Facility for Rare Isotope Beams will be performed in the near future.

Narwhals (Monodon monoceros) are sentinel species in the Arctic environment and are a vital component for Inuit culture and subsistence. The Arctic is undergoing rapid changes in temperature and sea ice cover and relatively little is known about how this has and will change narwhal foraging behaviour. There are three narwhal populations in the world, the Baffin Bay (BB), Northern Hudson Bay (NHB), and East Greenland (EG) populations; however, foraging behaviour, in terms of dive behaviour and primary dietary components, has really only been investigated in the BB population. Using a combination of stable isotopes, fatty acids, genetic techniques, and satellite tracking technologies I evaluated foraging behaviour in all three of the world’s narwhal populations. I also investigated social structure in the BB population to determine how adaptable narwhals are to a changing and dynamic Arctic environment. Stable isotopes (δ13C and δ15N) and fatty acids are chemical signatures in the tissues of an organism that can provide long-term information on their diet over varying temporal scales depending upon the tissue. Stable isotope analysis in the three narwhal populations found they forage on different primary prey, suggesting narwhal are adaptable in their preferred prey and that there is potential for them to adjust foraging behavior in the face of changing climate. Dietary changes were also assessed over three decades to determine how sea ice changes have affected narwhal foraging for the NHB and BB populations. Dietary changes were evident and can be attributed to changes in sea ice patterns and an altered migratory pathway for narwhals. An understanding of narwhal social structure is also needed to determine how behaviourally flexible narwhal are in diet and site fidelity. Genetic relatedness and dietary signatures from fatty acids were assessed for an entrapped group to determine if individuals that are closely related forage together, which would support a matrilineally driven social structure where females teach their young foraging strategies, and/or travel and forage together. I found no evidence that narwhals form a matrilineal social group, but they may display a fission-fusion structure, which may be an adaptation to patchy prey distribution in the Arctic. Finally, narwhal dive behaviour in all three populations was investigated to determine if dive behaviour could be used to predict diet. Dive differences among populations did correspond with differences in diet, suggesting that narwhals employ specialized foraging strategies. This has repercussions for their ability to adapt to ecosystem changes. Overall, narwhals may be more flexible in terms of their foraging behaviour than previously believed. However, an increased resilience to changing food webs will not be the only predictor of how narwhals will fare in the face of a changing climate; how they respond to increased industrial activities in their preferred habitats, increased predation from southern predators, and increased competition from southern cetaceans and humans alike, will play an equally large role in how they cope with the future.

The collection and analysis of a large number of belemnites and oysters with excellent biostratigraphic and diagenetic control has resulted in a highly detailed determination of the seawater Sr-isotope curve through the Jurassic and Early Cretaceous. The new data confirm the broad trends established by previous work, but the much sharper resolution of the new data allows the application of Sr-isotope stratigraphy with an optimal stratigraphic resolution of ± 1 to 4 ammonite subzones (± 0.5 to 2 Ma). The data show a general decline from the Hettangian (Early Jurassic) to a minimum in the Callovian and Oxfordian (Middle/Late Jurassic). This is followed by an increase through the Kimmeridgian (Late Jurassic) to a plateau reached in the Barremian (Early Cretaceous). In addition, there are major negative excursions in the Pliensbachian/Toarcian (Early Jurassic) and Aptian/Albian (Early Cretaceous). Stable isotope data collected from belemnites and oysters have resulted in the most extensive Jurassic δ¹³C and δ¹⁸O database to date. While both the carbon and oxygen data appear to give reasonable marine signals, the scatter in the data suggests that future research must document possible biological fractionation effects and develop better indicators for the diagenetic alteration of 613C and 6i 8O. The final chapter documents an unexpected correlation between sudden shifts in the Sr-isotope curve, the occurrence of positive 513C excursions, and the eruption of flood basalts. In the Jurassic and Cretaceous there is a correlation in time between sudden downward shifts in the Sr-isotope curve (Pliensbachian, Aptian, Cenomanian/Turonian), the occurance of positive 613C excursions, and the eruption of flood basalts. Each of these major downward shifts in the Sr-isotope curve is followed by a sudden upward shift, which although associated with a positive 613C excursion is not associated with an episode of flood basalt volcanism. In the Cenozoic the Sr-isotope curve no longer displays downward shifts, but the correlation continues between the occurrence of flood basalts and positive 513C excursions. Several lines of evidence suggest that the eruption of flood basalts is associated with pulses of hydrothermal activity, and that this hydrothermal activity brings about the conditions necessary for the genesis of carbon-burial events.

Standard geochemical analysis methods, such as aqueous geochemistry analysis and mineralogical analysis, frequently are utilized to evaluate the effectiveness of passive treatment systems, though they do not necessarily provide information regarding the mechanism of removal. Two emerging analytical techniques have shown promise by providing additional information to improve characterization of treatment systems: X-ray absorption spectroscopy (XAS) and stable isotope analysis. In this thesis, these novel analytical techniques were integrated with standard geochemical measurements to better characterize contaminated sites as well as potential treatment technologies used to mitigate aqueous contaminant mobility. Laboratory experiments were used to evaluate the removal of Se(VI) form simulated groundwater using granular Fe0 (GI) and organic carbon (OC). Greater than 90 % removal of Se(VI) was observed for systems containing GI after 5 days of reaction time and only 15 % removal was observed in systems containing OC. Synchrotron radiation-based XAS analysis of the treatment materials indicated the presence of both Se(IV) and Se(0) on the edges of GI grains after 6 hours reaction time, with no evidence of oxidized Se after 5 days of reaction. Several analytical techniques were integrated to characterize sediment contaminated with Hg and other contaminants through previous industrial practices. Analysis of the sediment by XAS indicated the possible presence of mercury selenide and copper sulfide. Resuspension tests were performed in oxic and anoxic conditions to simulate the effects of changing geochemical conditions of Hg release from sediments during dredging operations. The results indicated a higher release of Hg under oxic conditions in some sediment locations, suggesting that oxidative degradation of organic carbon or oxidative dissolution of Hg sulfides contributed to Hg release. The treatment of aqueous Hg(II) was evaluated with a variety of treatment media, including clay and GI. Treatment with GI was rapid, with 90 % removal observed after 2 hours reaction time. Extended X-ray absorption fine structure (EXAFS) analysis indicated the presence of Hg-O bonding on GI, suggesting that Hg was bound to Fe oxides formed on the surface of corroded GI. A new conceptual model for tracking the stable isotope fractionation of sulfur was coupled to the reactive transport model MIN3P to determine the effects of secondary transformations on sulfur cycling in passive treatment systems. Minor differences were noted when comparing the transport model-derived fractionation factor to calculations using a simplified Rayleigh distillation model, possibly indicating the effect of SO4 precipitation. The incorporation of stable isotope modeling provides a framework for the modeling of other isotope systems in treatment technologies.

This study focused on an invasive riparian reed grass, Arundo donax L., a clonal plant of the family Poaceae that is widely distributed in North America. Water availability, including water taken up from the roots locally or transported from the neighboring ramets, may affect the performance of A. donax in riparian zones. The first objective was to find out how moisture gradients affected the performance of A. donax in riparian zones. I measured leaf photosynthetic rate, leaf δ13C ratio, and plant growth-related parameters across two summer growing seasons at four transects perpendicular to the water course on the Rio Grande in South Texas. The second objective was to find out whether physiological integration existed in A. donax and how resource sharing, if any, affected plant growth. A rhizome severing experiment was conducted on five paired plots to compare growth-related parameters between plots with rhizomes severed and intact at 3, 7, and 11 weeks after treatment. Heavy water (δ 2H ~1800‰) was applied on three 1-m2 area over 3 successive days and rhizome samples were collected beyond the watering zone after 5, 24, and 48 hours of last watering. At short-term scales, A. donax performance was adversely affected by both drought and inundated conditions; over longer time scales, plant performance decreased as water availability declined in general, but biomass and stem density were similar across moisture gradients. I also found evidence of physiological integration in A. donax. Water was transported through interconnected rhizomes at least 3.5 m; transport distances averaged 1.67 m. Rhizome severing stimulated higher ramet production initially but over longer periods produced shorter thinner stems with lower flood tolerance. However, after 11 weeks of re-growth, plot-level biomass was similar between plots with severed and intact rhizomes. These results suggest that performance of A. donax is affected by water availability in riparian zones; however, clonal plant plasticity, water use efficiency, and clonal integration ameliorate impacts of water stress on the performance of A. donax. Such traits enhance its resource use, which could potentially increase competitive ability rate of establishment, and extent of this invasive species in heterogeneous riparian environments.

The present study aimed to determine whether stable isotope techniques can be universally applied to detect landfill leachate contamination in aquatic systems. Results of analysis of ��C in dissolved inorganic carbon ([delta]��C-DIC), deuterium and �⁸O in water ([delta]D-H₂O and [delta]�⁸O-H₂O), and �⁵N of dissolved inorganic nitrogen components ([delta]�⁵N-NH₄⁺ and [delta]�⁵N-NO₃⁻) were presented for leachate, surface, and ground water samples collected from seven landfills located throughout New Zealand between 2003 and 2006. The unique conditions within a landfill lead to measurable fractionations in the isotopic ratios of the products of degradation. Results of isotope and ancillary parameter analyses enabled the discernment of different types of leachate, resulting from different microbial processes within the landfill environment. The isotopic characterisation of leachate enabled improved interpretation of geochemical data from potentially impacted surface and ground waters, and provides useful insight to landfill development for landfill operators. A general isotopic fingerprint delineated by [delta]��C-DIC and [delta]D-H₂O values showed leachate to be isotopically distinct from uncontaminated surface and ground water for samples analysed in the present study. However, not all water samples identified as leachate-impacted via site-specific assessments exhibited isotopic values that overlapped with the general leachate fingerprint. This highlights the need to investigate each site individually, within the context of a possibly global leachate isotope signature. Site-specific investigations revealed the effectiveness of applying [delta]�⁸O-H₂O and [delta]�⁵N-NH₄⁺ or [delta]�⁵N-NO₃⁻, in addition to [delta]��C-DIC and [delta]D-H₂O analyses, to the detection of leachate impact on aquatic systems. Furthermore, ancillary parameters such as alkalinity and ammonium concentration enabled the construction of simple isotope mixing models for an estimate of the quantity of leachate contribution. Results of isotopic investigations of stream biota suggested potential for the development of bio-indicators to monitor leachate influence on aquatic ecosystems in landfill-associated streams. The present study demonstrated the probative power of stable isotope techniques applied to investigations of leachate impact on landfill-associated aquatic systems.