Individual specialization occurs when individuals selectively consume a subset of their population's diet. Intraspecific diet variation can stabilize population and community dynamics, promote species coexistence, and increase ecosystem productivity. Ecological variation also provides the variability necessary for natural or sexual selection to act. Individual threespine stickleback select different prey from a shared environment, and this variation is not simply a result of sex, size, or spatial heterogeneity. I use longitudinal observation of stickleback foraging microhabitat to support more commonly used cross-sectional metrics. Among recaptured individuals there were correlations between microhabitat use and functional morphology, and microhabitat use and long term dietary differences between individuals. I quantify individual specialization across populations using cross-sectional sampling to understand how and why ecological variation may itself be variable. All populations showed significant individual specialization. Specialization varied between populations and this variation seems to be a long-term property of populations. Overall morphological variance was positively correlated with ecological variation. Ecological variation, like all types of heritable variation, provides raw material for evolutionary change. For example, lacustrine populations of stickleback are commonly under disruptive selection due to intraspecific competition for prey resources. Speciation with gene flow may be driven by a combination of positive assortative mating and disruptive selection, particularly if selection and assortative mating act on the same trait. We present evidence that stickleback exhibit assortative mating by diet, using the isotopes of males and eggs within their nests. In concert with disruptive selection, this assortative mating should facilitate divergence. However, the population remains phenotypically unimodal, highlighting the fact that assortative mating and disruptive selection do not guarantee evolutionary divergence and speciation. There are several not-mutually-exclusive mechanisms by which assortative mating by diet may occur in these populations, such as shared microhabitat preference among individuals of similar diet. Stable isotopes reveal diet differences between different nesting areas and among individuals using different nest habitat within a nesting area. Spatial segregation of diet types may generate some assortative mating, but is insufficient to explain the observed assortment strength. We therefore conclude that sticklebacks' diet-assortative mating arises primarily from behavioral preference rather than from spatial isolation. / text

The stable isotope compositions (chlorine, oxygen, and hydrogen), major anion concentrations, and major/minor cation concentrations of 37 thermal (any spring water with temperature at least 6.5° C above mean ambient air temperature) and mineral springs from the Cascade volcanic arc system were measured in order to better determine chlorine sources within the Cascades hydrothermal systems, and thus place better constraints on halogen flux through the subduction zone. Typically, most subduction zone flux calculations have been limited to the study of the erupted magmas and gases from fumarole vents, yet magmatic discharge through thermal springs may be considerable, particularly those in the often ignored forearc. Additionally, 9 geochemically well characterized lavas from across the Mt. St. Helens/Mt. Adams region of the Cascade arc (Leeman et al. 2001, 2005) were analyzed for their halogen concentrations, as well as their Cl stable isotope composition. Cl concentrations in the thermal springs range from 6 to 13,850 ppm and have δ37Cl values that range from -0.1‰ to + 1.9‰ (average = +0.8 ± 0.4‰; error = ± 0.2‰), with no systematic variation along or across the arc. The slightly positive values (~0.0 to +0.9‰) may be explained by fluid-rock interaction with underlying lithologic units, such as 37Cl-enriched volcanic sequences, and/or serpentinites or oceanic crust of accreted oceanic terranes. Another process possibly contributing to these positive δ37Cl values, particularly those with δ37Cl > 1‰, is magmatic HCl fractionation during degassing generating an enriched 37Cl vapor which mixes with thermal waters. We cannot completely rule out slab-derived altered oceanic crustal chlorine that has degassed into the springs, although most slab Cl is believed to have already been devolatilized from the slab before reaching sub-arc depths corresponding to longitudes where these springs are located at the surface. Lavas from the Columbia transect across the arc exhibit highest Cl concentrations at the volcanic front compared to the forearc and backarc. Br, like Cl, exhibits highest concentrations along the volcanic front. F and I show a progressive decrease in concentration from forearc to backarc which may demonstrate the putative early surge of fluids/fluid mobile element loss early in subduction at relatively shallow depth. δ37Cl values range from -0.1 to +0.8‰ (error = ± 0.2‰) and may reflect a component of assimilation of crustal material, or is derived from an enriched mantle, although we cannot completely rule out some isotopic fractionation and/or slab-derived chlorine. / text

Seagrasses are extremely productive coastal plant communities that serve as habitat for various types of marine and estuarine fauna and provide numerous ecosystem services. Seagrass meadows around the world have become threatened by environmental and anthropogenic pressures such as altered hydrologic regimes, physical disturbances, and eutrophication. Monitoring programs that provide high-resolution information and document changes in cover, morphometric characteristics, species composition, and tissue nutrient content across large spatial scales are critical in global conservation and management efforts. In an attempt to address the uncertainties regarding the current distribution and condition of seagrasses in the southwest Gulf of Mexico, I conducted annual sampling from 2011-2013 to examine seagrass cover and condition at 558 permanent stations. Sampling occurred in three regions of the Texas coast: the Coastal Bend (CB), Upper Laguna Madre (ULM), and Lower Laguna Madre (LLM), which together comprise over 94% of the seagrasses in Texas. Significant trends in seagrass coverage and tissue elemental composition were highly location- and species-specific. In the CB, I did not observe significant changes in seagrass cover and no spatial patterns in tissue nitrogen (N) or phosphorus (P) were apparent. However, I observed a species shift in the northern ULM, where significant decreases in Syringodium filiforme cover were coupled with significant increases in Halodule wrightii cover. Long-term salinity records at four stations throughout the study area suggest that S. filiforme mortality in the ULM in 2013 was a product of an extended period of high salinity (> 55) that began in late 2012. In LLM, there were significant increases in H. wrightii cover in the north and significant decreases in T. testudinum cover in the south, which cannot be explained based on underwater light levels, salinity, or nutrient availability. Both H. wrightii and T. testudinum displayed lower C:N, C:P, and N:P ratios, along with enriched δ¹⁵N signatures nearest urban areas, particularly in the LLM. This study illustrates the value of integrating rapid-assessment field sampling and rigorous statistical and spatial analysis into a large-scale seagrass monitoring program to uncover patterns in seagrass community structure. I detected significant trends in seagrass coverage and condition across multiple spatial and temporal scales, including a massive species replacement that coincided with a prolonged period of hypersaline conditions.

Wasserverfügbarkeit ist in Wäldern Mitteleuropas wie auch in anderen Regionen der Welt oftmals ein limitierender Faktor für die Produktivität eines Bestandes. Ebenso wurde bereits in zahlreichen Studien untersucht, inwiefern Biodiversität einen Einfluss auf die Produktivität von Pflanzengemeinschaften hat. Es gibt jedoch nur wenig Informationen darüber, wie sich Baumartenvielfalt auf die Wassernutzung eines Waldbestandes auswirkt. Die Wassermenge, die für Transpiration und Zuwachs unter gegebenen Umweltbedingungen zur Verfügung steht ist davon abhängig, wie gut Pflanzen den vorliegenden Wasservorrat nutzen können. Es wird angenommen, dass Wasserverfügbarkeit für den Bestand durch komplementäre Wasseraufnahme zwischen gemeinsam auftretenden Pflanzenarten steigt. Daher zählt eine komplementäre Nutzung von Resourcen in ökologischen Studien allgemein zu den wichtigen funktionellen Effekten von Artenvielfalt. Jedoch setzt Komplementarität vorraus, dass funktionale Eigenschaften bestimmter Arten es diesen ermöglichen, entweder für andere Arten nicht verfügbare Resourcen zu nutzen, oder aber die selbe Resource räumlich und/ oder zeitlich getrennt voneinander zu nutzen. In gemischten Pflanzengemeinschaften ist oftmals eine erhöhte Produktivität im Vergleich zu Monokulturen zu beobachten, welche häufig durch Aufteilung von Resourcen und eine damit verbundene effektivere Nutzung erklärt wird. Im mitteleuropäischen Raum hat die Einrichtung von gemischten Laubwäldern in den letzten Jahrzehnten deutlich zugenommen. Gleiches gilt für die Umwandlung von Monokulturen (z. B. Fichte) in Bestände mit höherer Artenvielfalt, insbesondere von Arten die an die jeweiligen Standortbedingungen angepasst sind. Dieses Konzept der „naturnahen“ Forstwirtschaft zielt auf eine nachhaltige Produktion, erhöhte Stabilität angesichts möglicher extremer klimatischer Verhältnisse und eine Verbesserung der Erholungsfunktion von Wäldern ab. Infolgedessen ist es jedoch möglich, das Bestände mit erhöhter Baumartenzahl ebenso einen vergleichsweise höheren Verbrauch an Wasser aufweisen, was wiederum in erhöhtem Stress bei Trockenperioden resultieren könnte. Ein derartiger Effekt wäre demnach gegensätzlich zu den Zielen einer naturnahen Forstwirtschaft. Das Ziel dieser Studie war, die Auswirkung von Baumartenvielfalt (-mischung) auf die Wassernutzung eines temperaten Laubmischbestandes zu untersuchen und einen Beitrag zum besseren Verständnis dieser Zusammenhänge zu leisten. Hierfür wurden Untersuchungen innerhalb kleiner Baumgruppen durchgeführt, so genannter „Cluster“, die aus drei Bäumen der Kronenschicht bestanden, welche der potenziellen natürlichen Vegetation im Waldgebiet Hainich angehören (Fagus sylvatica, Tilia sp., Fraxinus excelsior, Acer pseudoplatanus, and Carpinus betulus). Die Cluster (n = 100) beinhalteten alle theoretisch denkbaren Kombinationen der 5 Untersuchungsarten in Ein- Zwei- und Dreiart Baumgruppen (25 Artkombinationen auf drei Diversitätsstufen), wobei jede Kombination in vier Wiederholungen vorlag (20 Einart-, 40 Zweiart- und 40 Dreiart-Cluster). In der ersten Studie wurde getestet, ob stabile Isotope von Wasser (2H und 18O) unter den gegebenen Bodenbeschaffenheiten im Hainich genutzt werden können, um die Wasseraufnahmetiefe von Bäumen zu identifizieren. Stabile Isotope von Wasser werden mittlerweile immer häufiger eingesetzt, um die Tiefe der Wasseraufnahme von Pflanzen festzustellen. Dabei wird ein Isotopengradient, der sich im Boden als Folge von Evaporation bildet, genutzt. Damit sich ein solcher Gradient bilden kann, benötigt es daher eine ausgedehnte Periode der Bodenaustrockung. Durch einen Vergleich der Isotopensignatur zwischen Wasserproben aus dem Stammxylem und verschiedenen Bodentiefen lässt sich die Tiefe der Wasseraufnahme der Bäume ermitteln. Allerdings lässt sich aus bisherigen Studien entnehmen das Bodeneigenschaften (z. B. Textur) die Signatur von 2H und 18O im Bodenwasser beeinträchtigen können. In Laborversuchen wurde daher getestet, ob eine Variation der Bodenfeuchte, des Tongehalts oder des Vorkommens von Calciumcarbonat im Boden eine Auswirkung auf die Isotopensignatur von extrahiertem Bodenwasser hat. Im ersten Versuch wurden getrocknete Bodenproben unterschiedlichen Tongehalts mit unterschiedlichen Mengen Wasser bekannter Isotopensignatur wiederbefeuchtet. Im zweiten Versuch wurde außerdem vor der Wiederbefeuchtung das Carbonat aus Teilproben des Bodens chemisch entfernt (Kontrollproben blieben unbehandelt), um den Effekt von Carbonat zu ermitteln. Für die Extraktion des Wassers aus den Proben wurde die kryogene Vakuum-Extraktion angewandt. Die Versuchsergebnisse deuteten darauf hin, dass mit abnehmendem Wassergehalt und zunehmendem Tongehalt in der Bodenprobe eine deutliche Veränderung von δ2H and δ18O im extrahierten Wasser auftrat. Weiterhin bewirkte die Anwesenheit von Carbonat im Boden eine Abreicherung von δ18O im Bodenwasser, wohingegen δ2H nicht verändert wurde. Den Ergebnissen Zufolge könnte der Einfluss eines hohen Carbonatgehalts im Boden so stark sein, dass eine unabhängige Anwendung von δ2H and δ18O zu widersprüchlichen Ergebnissen bei der Schätzung der Wasseraufnahmetiefe in hydrologischen Studien führen kann. Daher ist es zu empfehlen, deratige Analysen nicht nur auf einem, sondern auf beiden Isotopen zu stützen und auch die physikalischen sowie chemischen Bodeneigenschaften zu untersuchen. Da die erste Studie gezeigt hat, dass insbesondere 18O durch den Carbonatgehalt im Boden beeinflusst werden kann, wurde in der zweiten Studie ausschließlich die natürliche Abundanz von 2H genutzt, um die Wasseraufnahmetiefe einzelner Baumarten (Fagus sylvatica, Tilia sp. and Fraxinus excelsior) und deren Mischung während einer Periode der Bodenaustrocknung zu untersuchen. Hierbei sollte die Hypothese getestet werden, dass die Tiefe der Wasseraufnahme sich zwischen den Baumarten unterscheidet, was zu einer komplementären Wassernutzung in den Mehrart-Clustern führt. Weiterhin wurde angenommen, dass die Wasseraufnahmetiefe mit zunehmendem Baumdurchmesser ebenfalls ansteigt. Um die Tiefenverteilung der Wasserentnahme sowie mögliche Auswirkung der Baumgröße auf diese zu identifizieren, wurde die isotopische Zusammensetzung von Xylem- und Bodenwasserproben aus Einart- und Mehrart-Clustern analysiert und miteinander verglichen. Dafür wurden Bodenproben aus fünf Tiefenintervallen (0-0.1, 0.1-0.2, 0.2-0.3, 0.3-0.5, 0.5-0.7 m) in Stammnähe jedes untersuchten Baumes zusammen mit jeweiligen Stammproben entnommen. Mittels eines Isotopen Mischungsmodels konnte ermittelt werden, dass die relative Wasseraufnahmetiefe zwischen den Baumarten in Einart- sowie in Mehrart-Clustern variierte. Zusätzlich beeinflusste der Baumdurchmesser die Hauptaufnahmetiefe von Wasser in Mehrart-Clustern. Mit zunehmendem Durchmesser entnahmen die Bäume unabhängig von der Baumart Wasser vorwiegend aus vergleichsweise höheren Bodenschichten. Diese Resultate deuten auf eine Komplementarität in Bezug auf die relative Wasseraufnahme während einer Trockenperiode hin. Aufgrund des vorangegangenen Methodentests zu stabilen Isotopen wurde in dieser Studie lediglich 2H genutzt, um die Tiefe der Wasseraufnahme zu ermitteln. Zur Vollständigkeit wurde die Analyse jedoch auch mittels δ18O durchgeführt. Ebenso wie bei δ2H zeigte sich ein deutlicher Zusammenhang zwischen der Signatur der Hauptaufnahmetiefe und den Durchmessern der Bäume. Obwohl bei direktem Vergleich (grafische Analyse) und in der Modelberechnung δ2H and δ18O gegensätzliche Resultate zur relativen Wasseraufnahmetiefen der Bäume ergaben, ist der Zusammenhang zwischen Baumdurchmesser und Hauptiefe der Wasserentnahme gleich. Der letzte Teil der Studie befasste sich mit dem Einfluss unterschiedlicher Baumartenkombinationen, Artenvielfalt, Bestandesstruktur und klimatischen Bedingungen auf die Menge der täglichen Bodenwassernutzung während der Austrockungsperiode. Die Hypothese für diese Studie war, dass sich die Menge der täglichen Wasseraufnahme zwischen den Baumarten unterscheidet und mit ansteigender Baumartenvielfalt zunimmt (gemessen auf Einart- Zweiart-und Dreiart-Clustern). Die tägliche Wassaufnahme (mm Tag-1) wurde mittels eines einfachen Modelansatzes für die Bodentiefe von 0-0.3 m auf allen 100 Clustern und für die Tiefe 0-0.7 m auf 16 Clustern berechnet. Bis auf eine geringfügig höhere Wasseraufnahme in Einart-Clustern von Fraxinus excelsior im Zeitraum von Juni bis Mitte September 2009, konnte weder ein Einfluss der Artidentität der Bäume noch der Artenvielfalt auf die Menge der Wasseraufnahme in den Clustern festgestellt wurden. Die An- oder Abwesenheit der fünf untersuchten Baumarten in den Clustern zeigte ebenfalls kein Einfluss auf die Menge der Wasseraufnahme. Es lässt darauf schließen, dass unter den gegebenen Umständen Arteingenschaften und Artenvielfalt einen untergeordneten Einfluß auf die Nutzung von Bodenwasser haben, welcher möglicherweise auch von anderen Faktoren überdeckt wurde. Denkbar wäre hierbei ein Einfluss der Krautschicht oder die räumliche Anordnung der Bäume im Bestand, wobei die wichtigste Einflussgröße die vorherrschende Globalstrahlung war. Obwohl innerhalb der Cluster keine deutlichen Unterschiede gefunden wurden, die durch Arteigenschaften oder Artenvielfalt bedingt wurden, ist es dennoch möglich, dass diese auf einer größeren räumlichen Skala auftreten können. In Bezug auf die Wassernutzung eines Bestandes lässt sich demnach schliessen, dass Artenvielfalt alleine keine geeignete Vereinfachung für ein sehr komplexes Netzwerk aus verschiedenen Interaktionen zwischen Arteigenschaften innerhalb und zwischen Arten, sowie Bestandeseigenschaften und Umweltbedingungen ist. Jeder dieser Bestandteile könnte sich auf zeitlicher und räumlicher Ebene unterschiedlich auf die Wassernutzung eines Waldbestandes, unabhängig von der Biodiversität des Bestandes auswirken. Weiterhin ist es für Altbestände, mit geringem menschlichen Eingriff denkbar, dass sich Bäume im Laufe der Zeit gemäß der ihnen zur Verfügung stehenden Resourcen räumlich verteilen, wodurch ausgeglichene Nachbarschaftsbeziehungen entstehen könnten. Diese Arbeit zeigte, dass sich die physikalische und chemische Beschaffenheit des Bodens auf die Isotopensignatur von Wasser auswirkt. Dennoch können Isotopenversuche zur Ermittlung der Tiefenverteilung der Wasseraufnahme in temperaten Wäldern angewandt werden. Die Wasseraufnahmetiefe der Baumarten unterschied sich zwischen Ein- und Mehrart-Clustern, und deutete in Mehrart-Clustern auf eine Komplementarität hin, die durch Durchmesserunterschiede bedingt war. Baumartenvielfalt per se erhöhte jedoch nicht die Menge der absoluten Wasseraufnahme in den Clustern. Demnach gab es auch keinen Hinweis darauf, dass eine erhöhte Wassernutzungseffizienz zu einer deutlich verstärkten Ausnutzung der Bodenwasserresourcen während einer Austrocknungsperiode führt.

The metasupracrustal-hosted, often polymetallic REE-Fe-deposits of Bastnäs-type are found along the “REE-line” in the Palaeoproterozoic Bergslagen ore province, south central Sweden. They essentially comprise REE silicate-bearing magnetite skarn mineralisations with variable contents of other metals. Even though these deposits have been important for mining and research for centuries, their origin still remains unclear. In this study, samples from 10 different deposits along the REE-line have been charactarised as to mineralogy, petrography and bulk geochemistry, in addition to their isotope systematics. Mineral separates of magnetite and, when present, co-existing quartz or carbonates have been analysed for their oxygen and (for carbonates) carbon isotope compositions, in order to put constraints on the sources for metals and fluids in these deposits. Magnetites have δ18O-values of -1.79 to 1.12 ‰, while quartzes lie between 7.19 and 8.28 ‰. Carbonates have δ18O-values between 5.77 and 7.15 ‰ and δ13C-values between -5.35 and -3.32 ‰. Thermometric calculations based on mineral pairs (magnetite-quartz, magnetite-calcite/dolomite), combined with available fluid inclusion data, indicate formation of primary magnetite assemblages between c. 650 to 400 °C. At these temperatures, magnetites from some of the deposits would have been in equilibrium with a magmatic fluid (δ18O = 6-8 ‰), while magnetites from other deposits would have been in equilibrium with fluids of lower δ18O (4-6 ‰). Oxygen and carbon isotope trends in carbonates can be explained by interaction between original host carbonates and a fluid of magmatic composition. The combined results indicate that the Bastnäs-type magnetite-REE mineralisations were deposited from an originally magmatic fluid at relatively high temperatures. At local scale, variable modification of the fluid isotopic composition can be explained by mixing with seawater-dominated fluids.

Food webs are good ecological macro-descriptors and their study is important in ecology in understanding nutrient cycles, tracing and quantifying energy and in describing trophic interactions within an ecosystem. The knowledge of food web finds applications in various natural sciences disciplines but also in many productive sectors. This study investigated the structure of the food web of a shallow lake in the Pantanal flood plain. The food web included two macrophytes, six aquatic insects, four crustaceans and 24 fish species. Sources of carbon for the various organisms living in the lake were identified through the values of δ13C exhibited by the organisms. The δ15N signature was used to estimate the trophic position of each organism. A cluster analysis based on the two isotopic signatures revealed six different feeding guilds and emphasized on the broad occurrence of omnivory among animals living in the lake. This study revealed that the use of food carbon was the most important factor that structured the lake community. Very low values of δ13C in zooplankton, benthic dwellers and bottom-feeder organisms as well as similarities between the gradient of δ13C and that of use of methane oxidizing bacteria informed on the possible use of biogenic methane as a source carbon and energy for the lake biota.

The Pierina high-sulphidation epithermal Au-Ag deposit is located in the Cordillera Negra of north-central Perú, ~ 5km north of the coeval intermediate-sulphidation Ag–base metal Santo Toribio deposit, and in rocks of the Calipuy Supergroup. The deposit contains ~ 8 M oz Au, hosted in non-refractory iron oxides and, with heap-leach extraction, is one of the lowest-cost Au producers in the world. Stage Ia (15 Ma) and Ib (14.4 Ma) advanced-argillic alteration formed from mixed magmatic and meteoric waters. The main, 14.4 Ma event produced vuggy quartz alteration, focussed in a 16.9 Ma dacitic pumice-lithic tuff, and surrounded by quartz-alunite, quartz-dickite, and illite-montmorillonite alteration zones, the product of increased meteoric water contributions towards the periphery of the deposit. Stage II sulphide-barite mineralization introduced gold and silver, hosted submicroscopically in the disseminated high-sulphidation pyrite-enargite assemblage. Precipitation occurred from a low-to-medium - salinity magmatic fluid that mixed with meteoric waters at the site of ore deposition. A 14.1 Ma 40Ar/39Ar age for supergene alunite records the rapid incursion of meteoric waters into the deposit. The resulting oxidation of sulphides to schwertmannite, goethite, and hematite was facilitated by microbes, recorded by the stable-isotopic compositions of supergene barite+acanthite. Schwertmannite is enriched in Au and Ag and is the main precious-metal host. Regional pedimentation is inferred to have initiated retrograde boiling of the source magma chamber at 15 Ma, with renewed magma incursion triggering major alteration at 14.4 Ma. Both events involved the exsolution of an SO2-rich vapour and a more saline aqueous fluid. The latter migrated to Santo Toribio generating phyllic alteration and intermediate-sulphidation mineralization, whereas the SO2-rich vapours caused pyrite-bearing feldspar-destructive alteration along fluid pathways during ascent to Pierina. The subsequent single-phase, H2S-rich mineralizing fluid exsolved from the retracting magma at higher pressures. Vapour contraction during ascent along altered, unreactive pathways minimized the loss of S- and H+, optimizing the transport of Au as AuHS0. Watertable displacement resulting from pediment incision promoted the flow of groundwater into the epithermal environment where mixing with magmatic fluids precipitated gold. Supergene oxidation optimized conditions for microbial activity, a critical factor in the generation of economic mineralization. / Thesis (Ph.D, Geological Sciences & Geological Engineering) -- Queen's University, 2009-04-01 16:02:47.525

No description available.

Nitrous oxide (N???O) is a potent greenhouse gas, an important driver of climate change, and its concentration in the atmosphere is rising at an unprecedented rate. Agriculture is the leading contributor of all the anthropogenic N???O sources, and the vast majority of agricultural N???O emissions originate from soil. Of all the natural N???O emissions, two-thirds originate from soil and temperate forests contribute approximately one-sixth of the natural soil emissions. Consequently, there is great interest in understanding the soil nitrogen processes responsible for N???O production so that effective policies and management practises can be implemented to successfully mitigate climate change. The stable isotopes of nitrogen (N) and oxygen (O) in soil N???O emissions are hypothesized to be useful indicators of the biogeochemical processes that produce and consume N???O, and they may be used to apportion different environmental sources. The primary objective of this thesis was to assess the utility of ???????N and ???????O values to differentiate N???O produced by nitrification and denitrification. Most of the previous research on N???O isotopes has utilized microbial cultures of single organisms; yet natural systems contain a consortium of N-metabolizing microorganisms so the relevance of this early work to natural environments is uncertain. This thesis presents the results of experimental incubations of soil from an agricultural site and a temperate forest located within Ontario, Canada. Two well-drained soils (upland), two poorly-drained soils (wetland), and one stream sediment were incubated under varying conditions (temperature, moisture, and N-availability) to achieve a wide range in the rate of N???O production. The ???????N and ???????O values of N???O produced from the different experiments were characterized and the isotope effects (??) of N???O production were calculated. Experiments were conducted in aerobic or anoxic atmospheres to stimulate N???O formation by nitrification and denitrification, respectively. The ???????N-N???O produced by denitrification in all soils was 7???35??? lower than the ???????N-nitrate (NO??????). The ???????N-N???O produced by nitrification in the upland forest soil and the agricultural soils was 28???54??? lower than the ???????N-ammonium. Nitrification in the forested wetland soil yielded higher ???????N-N???O values (?? = ???16???), which was likely caused by an increase in the ???????N-substrate. With the exception of the latter soil, there was clear ?????N-separation between the nitrification- and denitrification-derived N???O in all soils. Consequently, ???????N values can be used to apportion different environmental sources of N???O on a site-by-site basis, provided that the rates of N metabolism are known and the isotopic endmembers are well-characterized. A novel approach was employed in this thesis to help unravel the key controls of ???????O-N???O and ???????O-NO?????? formation. Different ?????O-labelled soil waters were used to demonstrate that the abiotic exchange of oxygen atoms between water and nitrite (in equilibrium) is an important control of the ???????O-N???O formed by nitrifier-denitrification and the ???????O-NO?????? formed by nitrification. O-exchange in these incubations was highly variable between soils (37???88%) and it appeared to be rate-related. Furthermore, the ???????O value of microbial NO?????? is partially controlled by ?????O/?????O fractionation that occurs during O-exchange (equilibrium fractionation) and the uptake of molecular oxygen (O???) and water (H???O) (kinetic fractionation). This research showed that the ???????O value of microbially-produced NO?????? cannot be successfully predicted in soils based upon the commonly used ???one third, two-thirds rule???, which only takes into account the ???????O values of O??? and H???O. Successful predictions of ???????O-NO?????? using this rule appear to be fortuitous and are because of the range of ???????O-H???O at natural abundance and the magnitude of the isotope effects involved. Enzyme-catalyzed (biotic) O-exchange between water and nitrite/nitric oxide in denitrification was also quantified for the first time in soils. O-exchange during denitrification was significant and variable (39???95%), but uniquely confined to narrow ranges for each soil type. Almost complete O-exchange occurred in the well-drained agricultural and forested soils (86???95%); less O-exchange occurred in the agricultural and forested wetland soils (63???70%); and even less O-exchange occurred in the agricultural stream sediment (39???51%). The magnitude of O-exchange during denitrification was independent of soil temperature and moisture for a given soil, and it was not related to the rate of N???O production. This implies that the amount of O-exchange that occurs during soil denitrification is controlled by the dominant microbial community. For the first time, estimates of the net O isotope effect were determined for N???O production by soil denitrifiers that accounted for the complicating effects of O-exchange. The net ?????O-discrimination (N???O???NO??????) ranged between +32??? and +60???, with the exception of one treatment that was cooled (?? = +17???). The O isotope separation (??) that is actually observed in natural systems is often much lower, and in some cases negative. This is because the atomic O-exchange between water and nitrite/nitric oxide effectively diminishes the net ?????O separation between NO?????? and N???O because ???????O values of environmental water are usually lower than the ???????O values of N???O-precursors. The determinants of ???????O-N???O produced by nitrification pathways are complex and there is no holistic explanation of the O isotope dynamics in the literature. This thesis provides the first systematic model to describe ???????O-N???O formation by aerobic pathways. In addition to O-exchange between water and nitrite (at equilibrium), ???????O-N???O is controlled by ?????O/?????O fractionation that results from this O-exchange mechanism, and from fractionation that occurs during ammonia-oxidation and nitrite-reduction. Although explaining ???????O-N???O values produced by nitrification is complex, reports of nitrifier-derived ???????O-N???O in the literature and this thesis are narrowly confined between +13??? and +31??? (rel. VSMOW). This is distinct from much of the denitrifier-produced ???????O-N???O, which is often ?????O-enriched and higher than +33???. In three out of the five different soils investigated in this thesis, ???????O-N???O could be used to separate N???O formed by nitrification and denitrification. There was poor ???????O separation between nitrifier- and denitrifier-derived N???O in the well-drained soils because high amounts of biotic O-exchange and reduced O isotope separations yielded lower (predicted) estimates of denitrifier-produced ???????O-N???O. On the other hand, ???????N values could be used to apportion nitrifier- and denitrifier-derived N???O sources in these soils. Thus, stable isotope ratios of N???O are a valuable and promising tool that may help differentiate nitrifier-N???O from denitrifier-N???O in natural soil environments.

Invasive species are a known stressor on aquatic ecosystems, particularly in the waters of the Great Lakes basin. A recent invader, Hemimysis anomala, has had significant impacts on the food webs of Europe, where it invaded previous to its spread to North America. However, despite the fact that Hemimysis is now widespread in the Great Lakes basin, no analysis has been done on the trophic position of Hemimysis in North America invaded sites. This thesis used carbon (??13C) and nitrogen (??15N) stable isotopes to examine spatial and temporal patterns in Hemimysis trophic niche use in invaded North American sites in an attempt to broaden the knowledge base on this invader and to examine potential impacts this invader may have on the food webs of the Great Lakes. A spatial comparison of trophic niche use by Hemimysis among 13 sites in Lake Erie, Lake Ontario, and the St. Lawrence River was conducted between late July and mid-September of 2011. Main sources of carbon (benthic versus pelagic production) and trophic offset, or trophic distance from basal food web items, of Hemimysis were quantified using Hemimysis ??13C and ??15N values. Results indicated that: 1) Hemimysis relied predominantly on pelagic carbon sources at the majority of sites, and isotopic differences between life-stages existed at two of the 13 sites examined, 2) the trophic offset and reliance on pelagic food sources did not differ significantly between lotic and lentic sites, and 3) the isotopic niche width of Hemimysis was spatially heterogeneous, varying by an order of magnitude among sites, but was unrelated to the degree of isotopic variation in the basal food web at each site. Observed ranges in trophic offset and the pelagic fraction of dietary carbon indicate that Hemimysis derives carbon from both benthic and water column sources, as well as at multiple trophic levels. Results support the notion that Hemimysis is an opportunistic omnivore that displays significant dietary flexibility. To test the relative importance of key biotic and abiotic factors, taken from the literature, in driving Hemimysis isotopic variation, a temporal analysis was conducted at two North American sites, one in Lake Ontario and one in the St. Lawrence River, which were repeatedly sampled for Hemimysis and related food web items between September 2008 and January 2012. Seasonal patterns of winter enrichment ??? summer depletion were found in Hemimysis ??15N in Lake Ontario, but a similar pattern was not seen in the St. Lawrence River. Multiple regression models were used to determine the importance of water temperature, Hemimysis C:N ratios, Hemimysis length, and the isotopic values of basal food web components in explaining observed variation in Hemimysis ??13C and ??15N values. Significant relationships were found between Hemimysis isotopic values and water temperature, but relationships with the isotopic signatures of the pelagic basal food web were weak or nonexistent. Hemimysis ??13C values were significantly correlated with C:N ratios. Strong evidence of an ontogenetic dietary shift was found in Lake Ontario, with length showing a significant positive correlation with Hemimysis ??15N. All together the factors included in the models explained little of the observed variation in Hemimysis isotopic values, with approximately 20 % of the observed variation in Hemimysis ??13C, and just under half of Hemimysis ??15N variation, being explained by the included factors. As such, Hemimysis isotopic variation must be explained by factors not included in this study and may include factors such as species composition of the invaded site and availability of prey. Overall, the results of this thesis highlight the opportunistic and flexible nature of Hemimysis diet, and demonstrate the need for future work to determine the main drivers of isotopic variability and trophic niche selection of Hemimysis. The degree of trophic flexibility seen in Hemimysis implies that potential food web impacts will be site specific and heavily reliant on food web dynamics and environmental characteristics of the invaded site.