Dissertations / Theses on the topic 'Stable isotope tracers'

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.

Release of different nitrogen compounds can cause eutrophication in lakes and rivers whichcan lead to oxygen-free environments in bottom water and in the sediment and can in turnlead to fish-deaths. Ammonium can be toxic to biota and nitrate can in high concentrationeven be toxic to humans. WHO has released a limit for nitrate concentration in drinking waterof 10mg/l. The LKAB mine in Kiruna is the largest underground iron mine in the world and isprospecting, mining and refining iron ore, with an annual production of around 28 milliontons. Release of different nitrogen compounds as a result of the explosives used during themining operations has been a known problem for some time; however the processes affectingnitrogen during the water transport have never been fully investigated. The main objective of this MSc thesis is to determine if changes in nitrogen and oxygenisotope composition can be used as a tracer for nitrogen transformation processes in the minewater at LKABs underground mine in Kiruna. Water samples were collected at key points in the water transport system and were analyzedfor isotopic composition. Isotopic and chemical data revealed two different sources of nitrateand ammonium, undetonated explosives and leachate from waste rocks. Three differentnitrogen changing processes affecting concentration of nitrate and ammonium were found:ammonium volatilization, nitrification and sorption. It was not possible to quantify theseprocesses individually. No processes which decrease the nitrate concentration were found.

This thesis has developed a suite of compound specific stable isotope tools to monitor landfill leachate and identify the infiltration of leachate to ground water and surface water. These tools have the power to indicate the fractional contribution multiple discrete sources of pollution are making to a single location. This journey began by developing two solid phase extraction (SPE) methods to extract non-polar and polar organic compounds from leachate with minimal fractionation of hydrogen or carbon isotopes. Non-polar compounds were successfully extracted using ENV+ SPE cartridges and polar compounds were successfully extracted using Strata-X SPE cartridges. The isotopic fractionation of non-polar compounds during ENV+ extraction varied significantly (up to 245⁰/₀₀ and 1.8⁰/₀₀ for D and ��C respectively, when eluted with acetonitrile and ethyl acetate, as recommended by manufacturers) but the fractionation of compounds eluted with dichloromethane was negligible (less than instrumental precision). Polar compounds were eluted from Strata-X cartridges with negligible isotopic fractionation using methanol. The direct comparison of SPE and liquid-liquid extraction found SPE to extract slightly more compound from leachate then liquid-liquid extraction (especially for polar compounds) and the isotopic compositions of compounds did not change with extraction methods. These new analytical methods subsequently were used to determine the isotopic compositions of organic compounds dissolved in leachates from three New Zealand landfills. The molecular and isotopic signature of leachate varied significantly between landfills, indicating the isotopic fingerprint of organic compounds in leachate is unsuitable as a universal tracer of leachate. However, compounds such as terpien-4-ol, methylethylbenzene and juvabione maintained their isotopic composition over short geographical distance-indicating their potential as site-specific tracers of leachate. Organic compounds analysed on a transect across the landfill boundary indicated polar compounds were more mobile than semi-volatile compounds and possessed a more conservative isotopic composition. However, hexadecanoic acid extracted from leachate and ground water was highly depleted in ��C (-72 ⁰/₀₀ to -40⁰/₀₀), indicative of methanogenic and sulfate reducing bacteria. These bacteria only live in highly reducing environments such as leachate; therefore their presence in the pristine environment can potentially indicate the release of leachate from the landfill. The final experiments traced the uptake and utilisation of leachate by periphyton. The isotopic composition of bulk periphyton, fatty acids and phytol indicated that microbial assimilation and utilisation of nutrients is a complex process. Fatty acid biomarkers for green algae and diatoms showed signs of leachate derived nutrients, however the availability of nutrients (carbon, nitrogen, water and light) caused significant changes in metabolic processes and isotopic compositions. Under slow growing conditions, the [delta]��C composition of periphyton became enriched in ��C as solar irradiation levels decreased (including shading by detritus and periphyton), while the [delta]D composition of fatty acid was controlled by the internal recycling of hydrogen. This study indicated the power of compound specific isotope analysis as a tool to detect the release of landfill leachate from a landfill, especially at locations with multiple potential sources of contaminants, and provides a sound platform for future research.

This dissertation investigated the physical and biogeochemical processes affecting the source, fate, and transport of sediment, carbon, and nitrogen within a highly-coupled fluviokarst system. Elemental and isotopic datasets were collected at surface and subsurface locations for both dissolved and particulate contaminant phases, new methodology regarding data collection was presented to the karst research community, an in-cave sediment transport model coupling physical transport with elemental and isotopic mass balances of carbon and nitrogen was formulated, pathway and process control on nitrate leaching from agricultural karst watersheds was assessed, and nitrate mobilization and fractionation were modeled using high frequency storm sampling and long-term low-flow sampling. Data and modeling results indicate that phreatic karst conduits are transport-limited during hydrologic events and experience subsurface deposition of labile, storm-injected sediment which is subsequently decomposed by heterotrophic bacteria. An estimated 30% of the organic carbon associated with sediment is decomposed during transport in the subsurface karst. Concentrations of nitrate in subsurface waters are consistently 50% greater than surface inputs suggesting an additional source of subsurface nitrate. Further modeling of nitrate leaching indicates that quick-flow water sources dilute nitrate concentrations and slow-flow (epikarst and phreatic) sources account for approximately 90% of downstream nitrate delivery. Field sampling of extreme events highlights the physical transport and delayed release of high nitrate concentrations by intermediate karst pathways, which is likely associated with a transition from epikarst to soil drainage during storm recession. Modeling of sediment carbon and nitrogen within the karst SFGL supports the idea that the cave sediment bed experiences hot spots and hot moments of biogeochemical activity. Sediment nitrogen tracing data show a significant increase in δ15NSed at the spring outlet relative to karst inputs indicating the potential for isotope fractionation effects during dissolved N uptake by cave biota. Dissolved nitrogen stable isotopic composition shows a significant downstream decrease in δ15NNO3 within the conduit, likely associated with nitrification. Data and modeling results of sediment, carbon, and nitrogen emphasize the role of multiple pathways, turbulent transport, and in-conduit transformations in controlling contaminant flux from karst watersheds.

The purpose of this study was to compare the anabolic response to acute running exercise in two different leg muscles in endurance-trained men using two different stable isotope tracers. 6 male subjects (26±2 yr; V02max 63±2 ml•kg-' •min-') performed a 45 min treadmill run at 77±1 % intensity. Infusions of d3-leucine and d5-phenylalanine were used to measure mixed muscle FSR at rest and 24 hr post-exercise. An additional infusion of 10% amino acid solution was added to the post-exercise infusion to maximize the muscle anabolic response. Muscle biopsies were obtained from the vastus lateralis (VL) and soleus (SOL) at 2 and 6 hr of the infusion for the measurement of isotope incorporation. Additional muscle biopsies were obtained prior to and 4 hr post-exercise for determination of muscle glycogen use. At rest FSR was similar between the VL and SOL using either tracer (p>0.05). At 24 hr post-exercise FSR was elevated in both muscles, independent of the tracer used (p<0.05). Muscle glycogen was decreased to the same extent in both muscles by -31% at 4 hr post-exercise (p<0.05). These data suggest that the VL and SOL muscles are both stimulated similarly during 45 min of level grade running. Additionally, both muscles respond similarly 24 hr post-exercise, independent of the tracer used for the determination of protein synthesis.
School of Physical Education, Sport, and Exercise Science

Phenylketonuria (PKU) is an inherited inborn error of phenylalanine (PHE) metabolism caused by deficiency of hepatic enzyme phenylalanine hydroxylase (PAH). Therefore, PHE accumulates in plasma leading to mental retardation and developmental delay. Kuvan® (Sapropterin dihydrochloride), a synthetic form of tetrahydrobiopterin (BH₄), has been shown to reduce plasma PHE levels in PKU, but not all patients respond to sapropterin treatment. The major mode of treatment remains nutritional management with dietary restriction of PHE and provision of sufficient protein. The dietary protein requirement in children with PKU remains unknown. Therefore the objectives of the current thesis were: 1) to identify sapropterin responsiveness in PKU children using a minimally invasive L-[1-¹³C] phenylalanine breath test (¹³C-PBT), and 2) to determine protein requirements in PKU children using the indicator amino acid oxidation (IAAO) technique. Experiment 1- Nine children with PKU (5-18y) underwent ¹³C-PBT tracer protocols twice, once before and once after 1-2 weeks of sapropterin therapy. ¹³CO₂ was measured using isotope ratio mass spectrometer (IRMS). The study protocol was tested in healthy children (n= 6) as proof of principle. Experiment 2- Four PKU children (5-18y) were recruited to participate in test protein intakes (ranging from deficiency to excess 0.2 – 3.2 g/kg/d) with the IAAO protocol using L-[1-¹³C] leucine, followed by collection of breath and urine samples over 8 hours. Results 1- ¹³CO₂ productions in all children with PKU pre-sapropterin treatment were low, except in one child (PKU04). Five children with PKU showed a significantly higher peak enrichment after sapropterin treatment at 20min. Three PKU children had no change in ¹³CO₂ production post sapropterin therapy. Results 2- The mean protein requirement, identified using 2-phase linear regression analysis was determined to be 1.85 g/kg/d. This result is significantly higher than the most recent PKU recommendations (2014) (1.14 – 1.33g/kg/d, based on 120-140% above current recommended dietary allowance RDA). These findings show that the ¹³C-PBT can be a minimally invasive method to examine in vivo PHE metabolism in PKU children responsive to sapropterin therapy. Also, current recommendations for optimal protein intake may be underestimated.
Land and Food Systems, Faculty of
Graduate

The discharge of groundwater into surface water bodies is a hidden, but significant pathway for the input of water and matter into lakes, rivers, estuaries and the coastal sea. Since groundwater is most often characterized by higher levels of nutrients or heavy metals, its discharge has often a crucial effect on the surface water body´s chemistry and the ecosystem health as well as on the related ecosystem service supply. For instance, groundwater-derived nutrient inputs are essential to fuel primary productivity, but if critical thresholds are exceeded groundwater-derived nutrient inputs can cause eutrophication, which may trigger harmful algal blooms or the creation of oxygen minimum zones – a serious threat to aquatic life. This thesis focuses on quantifying submarine and lacustrine groundwater discharge by applying environmental tracer based methods with emphasis on radionuclide (radon and radium isotopes) and stable water isotope (δ18O, δ2H) techniques. These tracers are suitable for determining groundwater discharge as they show distinct concentration and isotope ratio gradients between groundwater and the receiving surface water. Four studies are presented in this thesis: (1) The quantification of the response delay of the mobile radon detector RAD7 applied for radon-in-water mapping. The response delay of the mobile radon-in-air detector RAD7 is determined for two detection set-ups (radon extraction via RADaqua and via a membrane module) as well as for a range of water flow rates. For the membrane module the response delay is less pronounced compared to the RADaqua. For instance, at a water flow rate of 1 l min-1 the peaks of the instruments recordings lag behind the radon-in-water concentrations by ~10 min for the membrane module and by ~18 min for the RADaqua. Further, it was demonstrated that faster water flow rates decrease the response delay. An algorithm is presented that allows the inverse calculation of radon-in-water concentrations from RAD7 records for the described detection set-ups and water flow rates. Thus, it allows a more precise localization of radon-in-water anomalies and, consequently a more precise localization of groundwater discharge areas. (2) Determination of submarine groundwater discharge into a large coastal bay (False Bay, South Africa) SGD consists generally of two components: (a) fresh terrestrial SGD (FSGD) driven by the inland hydraulic gradient and (b) seawater re-circulation (RSGD) through the coastal aquifer driven by seaward effects such as tidal pumping. A bay-wide radon mapping resulted in identification of a SGD site, where subsequently detailed investigations were conducted. At this SGD site a salt and a radon mass balance were applied consecutively for determining FSGD and total SGD, respectively. RSGD was inferred from the difference between FSGD and total SGD. For the radon mass balance, new approaches for calculating the radon degassing and mixing loss were proposed. The tracer mass balance revealed median FSGD of 2,300 m³ d-1 or 0.9 m³ d-1 per m coastline and median RSGD of 6,600 m³ d-1 or 2.7 m³ d-1 per m coastline. The FSGD rate was validated using (a) a hydrological model for calculating the groundwater recharge rate and (b) a groundwater flow model for delineating the subsurficial FSGD capture zone. This validation supported the tracer based findings. The relevance of this study is foremost the presentation of new methodological approaches regarding the radon mass balance as well as the validation of FSGD under consideration of hydrological and hydrogeological information. (3) Differentiation of fresh and re-circulated submarine groundwater discharge in an estuary (Knysna Estuary, South Africa) Knysna Estuary is a more complex system than False Bay since besides seawater, FSGD and RSGD also river water mixes within the estuary. Both FSGD and RSGD were differentiated by applying a mixing analysis of the estuary water. For this purpose, an end-member mixing analysis (EMMA) was conducted that simultaneously utilizes radon and salinity time series of estuary water to determine fractions of the end-members seawater, river water, FSGD and RSGD. End-member mixing ratio uncertainty was quantified by stochastic modelling (Monte Carlo simulation) under consideration of end-member characterization uncertainty. Results revealed highest FSGD and RSGD fractions in the estuary during peak low tide. Median fractions of FSGD and RSGD were 0.2 % and 0.8 % of the estuary water near the mouth over a 24 h time-series. In combi-nation with a radon mass balance median FSGD of 46,000 m³ d-1 and median RSGD of 150,000 m³ d-1 were determined. By comparison to other sources, this implies that the SGD is a significant source of dissolved inorganic nitrogen (DIN) fluxes into the estuary. This study demonstrates the ability of EMMA to determine end-member fractions in a four end-member system under consideration of end-member uncertainty. Further, the importance of SGD for the water and DIN budget of Knysna Estuary was shown. (4) Quantification of groundwater discharge and water residence time into a groundwa-ter-fed lake (Lake Ammelshainer See, Germany). The presented approach utilizes the stable isotopes of water (δ18O, δ2H) and radon for determining long-term average and short-term trends in groundwater discharge rates. The calculations were based on measurements of isotope inventories of lake and groundwater in combination with climatic and isotopic monitoring data (in precipita-tion). The results from steady-state annual isotope mass balances for both δ18O and δ2H are consistent and reveal an overall long-term average groundwater discharge that ranges from 2,800 to 3,350 m³ d-1. These findings were supported by the good agree-ment of the simulated annual cycles of δ18O and δ2H lake inventories utilizing the de-termined groundwater discharge rates with the observed lake isotope inventories. However, groundwater discharge rates derived from radon mass balances were signifi-cantly lower, which might indicate a distinct seasonal variability of the groundwater discharge rate. This application shows the benefits and limitations of combining δ18O/δ2H and radon isotope mass balances for the quantification of groundwater con-nectivity of lakes based on a relatively small amount of field data accompanied by good quality and comprehensive long-term meteorological and isotopic data (precipitation). This thesis presents important methodological achievements with respect to radon and stable water isotope mass balances, uncertainty quantification, geochemical differentia-tion between FSGD and RSGD and validation of FSGD. Further, first SGD estimates are reported for False Bay and Knysna Estuary in South Africa
Der Austritt von Grundwasser in Oberflächengewässer stellt einen unsichtbaren Ein-tragspfad von Wasser und Stoffen in Seen, Flüsse, Ästuare und das küstennahe Meer dar. Die Konzentrationen vieler Stoffe wie beispielsweise von Nährstoffen und Schwermetallen ist im Grundwasser im Allgemeinen signifikant höher als in Oberflächengewässern. Daher können selbst volumetrisch verhältnismäßig kleine Grundwasseraustritte entscheidenden Einfluss auf Wasserchemie und den Gesundheitszustand des aquatischen Ökosystems haben, womit Auswirkungen auf die Bereitstellung von Ökosystemleistungen verbunden sein können. Beispielsweise sind grundwasserbürtige Nährstoffeinträge eine entscheidende Steuergröße für die Primärproduktivität. Überschreiten diese grundwasserbürtigen Nährstoffeinträge jedoch einen Schwellenwert, kann es zur Eutrophierung des Oberflächengewässers kommen. Dies wiederum kann toxische Algenblüten oder die Entstehung von Sauerstoffminimumzonen zur Folge haben und das aquatische Leben bedrohen. Diese Dissertation beschäftigt sich mit Methoden zur Quantifizierung von Grundwas-sereinträgen in den küstennahen Ozean, Ästuare und in Seen. Dabei stützt sich diese Arbeit primär auf Umwelttracer, vor allem auf Radionuklide (Radon- und Radium-Isotope) sowie die stabilen Isotope des Wassers (δ18O, δ2H). Diese Umwelttracer sind für die untersuchten Systeme in besonderer Weise geeignet, da zwischen Grundwasser und Oberflächenwasser ein ausgeprägter Gradient hinsichtlich Konzentration bzw. Isotopensignatur besteht. Vier Einzelstudien stellen den Kern dieser Arbeit dar: (1) Die Quantifizierung der Antwortverzögerung des mobilen Radon-Detektors RAD7, an-gewendet für die Radon-in-Wasser-Kartierung. Die Antwortverzögerung des mobilen Radon-in-Luft-Detektors RAD7 wurde für zwei Messanordnungen (Radonextraktion via RADaqua und via Membranmodul) sowie für einen Bereich von Wasserdurchflussraten bestimmt. Für die Radonextraktion via RADaqua ist die Antwortverzögerung stärker ausgeprägt als für das Membranmodul. Bei einer Wasserdurchflussrate von 1 l min-1 treten die Peaks der aufgezeichneten Werte ~10 min nach den Radon-in-Wasser Peaks auf, während die Verzögerung bei Radonextraktion via RADaqua ~18 min beträgt. Weiterhin wurde eine Reduktion der Antwortverzögerung mit zunehmenden Wasserdurchflussraten beobachtet. Der vorgestellte Algorithmus ermöglicht in Kombination mit den berechneten Radontransfer-Koeffizienten die inverse Modellierung der Radon-in-Wasser-Konzentrationen, basierend auf den RAD7-Messwerten. Dies ermöglicht beispielsweise eine genauere Lokalisierung von räumlichen Radon-in-Wasser Anomalien und folglich eine präzisere Bestimmung von Grundwasseraustrittsstellen. (2) Quantifizierung untermeerischer Grundwasseraustritte in eine große Meeresbucht (False Bay, Südafrika) Untermeerische Grundwasseraustritte (“Submarine Groundwater Discharge” – SGD) bestehen aus zwei Komponenten: (a) Süßwasser-SGD (“Fresh SGD” – FSGD) angetrieben durch den meerwärtsgerichteten hydraulischen Gradienten, und (b) re-zirkuliertem SGD („re-circulated SGD“ – RSGD), verursacht durch Prozesse wie gezeitengesteuerte Infiltration von Meerwasser in den Aquifer. Eine Radon-Kartierung entlang der gesamten Küstenlinie der Bucht führte zur Lokalisierung von SGD, woraufhin dort vertiefende Untersuchungen durchgeführt wurden. In diesem Bilanzgebiet wurden eine Salz- und eine Radon-Massenbilanz durchgeführt, um FSGD bzw. Gesamt-SGD zu bestimmen. RSGD wurde aus der Differenz von FSGD und SGD abgleitet. Für die Radon-Massenbilanz wurden neue Ansätze für die Berechnung der Radon-Entgasung in die Atmosphäre und des Radon-Mischungsverlustes mit küstenfernerem Wasser präsentiert. Die Tracer-Massenbilanzen ergaben einen FSGD-Median von 2.300 m³ d-1 bzw. 0,9 m³ d-1 pro Meter Küstenlinie und einen RSGD-Median von 6.600 m³ d-1 bzw. 2,7 m³ d-1 pro Meter Küstenlinie. Die FSGD-Rate wurde mit Hilfe eines hydrologischen Modells zur Abschätzung der Grundwasserneubildungsrate und eines Grundwasserströmungsmodells zur Abgrenzung des unterirdischen Einzugsgebiets des Bilanzraums bestimmt. Diese unabhängige Methode bestätigte die Tracer-basierten Ergebnisse. Die Bedeutung dieser Studie besteht zuvorderst in der Vorstellung neuer methodischer Ansätze bei der Radon-Massenbilanzierung sowie in der Validierung von FSGD unter Berücksichtigung hydrologischer und hydrogeologischer Daten. (3) Unterscheidung von FSGD und RSGD in einem Ästuar (Knysna Ästuar, Südafrika). Das Knysna-Ästuar ist hinsichtlich der Bestimmung von SGD im Vergleich zur False Bay ein komplexeres System, da sich neben Meerwasser, FSGD und RSGD auch Flusswasser in signifikanten Mengen im Ästuar mischt. FSGD- und RSGD-Anteile wurden anhand der chemischen Zusammensetzung des Ästuarwassers unterschieden. Für diesen Zweck wurde eine End-Member-Mischungsanalyse (EMMA) auf Grundlage von Radon- und Salinitätszeitreihen des Ästuarwassers durchgeführt. Durch ein Optimierungsverfahren wurde die Mischung der End-member Meerwasser, Flusswasser, FSGD und RSGD für jeden Zeitschritt mit dem Ziel der bestmöglichen Übereinstimmung mit den gemessenen Radon- und Salinitätszeitreihen bestimmt. Die Unsicherheit in der Bestimmung der End-member-Anteile wurde durch stochastische Modellierung (Monte-Carlo-Simulation) quantifiziert. Die höchsten Anteile von FSGD und RSGD traten bei Niedrigwasser auf. Die mittleren Anteile von FSGD und RSGD betrugen in der Nähe der Ästuarmündung 0,2 % und 0,8 % während einer 24-stündigen Zeitreihenmessung. Diese Informationen führten in Kombination mit einer Radon-Massenbilanz zur Bestimmung eines mittleren FSGD von 46.000 m³ d-1 sowie eines mittleren RSGD von 150.000 m³ d-1. Diese Ergebnisse implizieren unter Einbeziehung weiterer Daten, dass SGD ein bedeutender Pfad für den Eintrag von gelöstem anorganischem Stickstoff (DIN) in das Knysna-Ästuar darstellt. Diese Studie zeigt das Potenzial einer EMMA für die Bestimmung der Anteile von vier End-membern unter Nutzung von zwei gemessenen Variablen und unter Berücksichtigung der End-member-Unsicherheit. Außerdem wurde die Bedeutung von SGD für das Wasser- und DIN-Budget des Knysna-Ästuars aufgezeigt. (4) Quantifizierung von Grundwasseraustrittsrate und Wasserverweilzeit eines grundwas-sergespeisten Sees (Ammelshainer See, Deutschland). Der vorgestellte Ansatz nutzt die stabilen Isotope des Wassers (δ18O, δ2H) und von Ra-don für die Bestimmung des mittleren langfristigen sowie der aktuellen Grundwas-seraustrittsrate. Die Berechnungen beruhen auf Abschätzungen des Isotopeninventars anhand von Feldmessungen, der Isotopensignatur des Grundwassers sowie ergänzen-den Klima- und Isotopen-Daten (Niederschlag). Die Ergebnisse einer stationären Isoto-pen-Massenbilanz für δ18O und δ2H sind übereinstimmend und ergaben einen langfristigen mittleren Grundwasseraustritt von 2.800 bis 3.350 m³ d-1. Dieses Ergebnis wurde für die Modellierung des jährlichen Zyklus des Isotopeninventars im See benutzt, welches mit den gemessenen Isotopenwerten konsistent ist. Die auf Grundlage einer Radon-Massenbilanz abgeleiteten aktuellen Grundwasserzutrittsraten lagen im Gegensatz dazu deutlich niedriger, was jedoch nicht notwendigerweise einen Widerspruch darstellen muss, sondern vielmehr ein Hinweis auf eine möglicherweise ausgeprägte saisonale Variabilität des Grundwasseraustritts darstellen kann. Diese Studie zeigt Möglichkeiten und Grenzen der Anwendung von einer Kombination aus δ18O/δ2H- und Radon-Massenbilanzen für die Bestimmung der Grundwasseranbindung von Seen mit einem vergleichsweise geringen Messaufwand unter Nutzung qualitativ hochwertiger und umfangreicher Klima-und Isotopen-Daten (Niederschlag). Diese Dissertation präsentiert wichtige methodische Fortschritte hinsichtlich der An-wendung von Radon- und stabilen Isotopen-Massenbilanzen, der Quantifizierung von Unsicherheit, der Unterscheidung von FSGD und RSGD anhand geochemischer Daten und der Validierung von FSGD. Außerdem wurden erstmals SGD-Raten für Standorte in Südafrika (False Bay und Knysna-Ästuar) vorgestellt

Glucose and ketones are important energy substrates in the human body and brain. Their use is highly regulated depending on energy status which can vary according to multiple factors such as type of cell, fed or fasted state, type of diet, or health state. Use of either substrate is also subject to multiple homeostatic feedback loops. Energy substrate availability has implications in several disorders including declining cognitive function in the elderly. While glucose availability is known to decrease in elderly with cognitive deficits, it is unclear whether this also occurs in healthy elderly, either in the body or brain. Also unknown is whether, in healthy elderly, the use of ketones as energy substrates is affected, and whether ketones could be used as an alternative energy substrate in situations of a decline in glucose availability. A clearer understanding of the use of glucose and ketones in aging is necessary to determine whether declining energy substrate availability that may occur in the elderly is a contributing factor to cognitive deficits, a result of cognitive pathology, or simply a feature of the physiological aging process. Objective. The overall goal of the laboratory where this research was carried out is to ascertain whether alternate energy sources to glucose, i.e. ketones, may help alleviate the risk of declining cognitive function during aging. The specific objective of the research project presented in this thesis was to evaluate the metabolism of glucose and ketones in the healthy elderly compared to young or middle age subjects during mild, short-term ketosis induced by a ketogenic breakfast. Results. Elderly people in relatively good health have a similar capacity to produce ketones and to oxidize [superscript 13]C-glucose and [superscript 13]C-β-hydroxybutyrate as middle-aged or young adults. Discussion. The results of this project encourage further exploration of whether ketones could be used as and alternative energy substrate to glucose as, at least in healthy elderly, there is no impedance of raising plasma ketones in response to a ketogenic intervention. // Résumé : Introduction. Le glucose et les cétones sont des substrats énergétiques importants pour le corps et le cerveau humain. Leur utilisation est spécifiquement régulée selon I'état énergétique qui varie en fonction du type de cellule, de I'état nourrie ou à jeun, du type de diète, de I'état de la santé. L'utilisation est également régulée par des voies de rétrocontrôle homéostatique. La disponibilité des substrats énergétiques est impliquée dans plusieurs désordres, dont le déclin des fonctions cognitives, chez les personnes âgées où une diminution de la disponibilité du glucose est démontrée. Cependant, il n'est pas encore connu si cette diminution est présente chez les personnes âgées en bonne santé ; soit dans le corps ou le cerveau. La capacité d'utiliser les cétones comme substrats énergétiques chez les personnes âgées saines et la possibilité d'utiliser les cétones comme substrat énergétique alternatif dans le cas d'un déclin de la disponibilité de glucose sont inconnues. Une meilleure compréhension de I'utilisation du glucose et des cétones sera nécessaire pour clarifier si une diminution de la disponibilité des substrats énergétique contribue au déclin cognitif, se manifeste à la suite des pathologies cognitives, ou encore est simplement une caractéristique du processus physiologique du vieillissement. Objectif. L'objectif principal du laboratoire est de déterminer si les sources d'énergie alternatives au glucose, c'est-à-dire les cétones, pourraient ralentir le déclin cognitif chez les personnes âgées. L'objectif du projet de recherche de ce mémoire était d'évaluer le métabolisme du glucose et des cétones chez les sujets âgés, d'âge moyen, et jeune après la prise d'un déjeuner induisant une faible cétogénèse de courte durée. Résultats. Les personnes âgées en santé ont une capacité similaire au sujet d'âge moyen et jeune à produire des cétones et à oxyder le [indice supérieur 13]C-glucose et le [indice supérieur 13]C-β- hydroxybutyrate. Perspectives. Les résultats de ce projet incitent à continuer à explorer si les cétones pourraient être utilisés comme substrats énergétiques afin de contourner le problème d'un déclin de I'utilisation du glucose, car il n'y a aucun obstacle dans la production des cétones suite a une intervention cétonique chez des sujets âgées en bonne santé.

Forested areas have been cited for their highly diverse floral and faunal assemblages, which are currently under threat from anthropogenic activities that restrict their range and deplete the resources produced within these naturally fragmented patches. Historically, up to 67 percent of avifaunal species associated with well-treed areas have undergone localised extinctions, consequentially affecting biodiversity as a measure of species richness and ecosystem functionality. To date, more than 900 of the bird species affiliated with forests are under threat and despite the theory surrounding functional redundancy, the mass extinction that is currently underway poses considerable limitations on the ecological integrity of these biomes. In South Africa, indigenous forest (one of the rarest biomes), occurs predominantly in small isolated patches along the eastern escarpment. With mountainous terrain emphasised as ‘prominent hotspots of extinction’, the limited dispersal and habitat sensitivity of montane forest fauna renders these species more prone to localised extinctions. BirdLife International, the IUCN and SABAP2 all indicate reductions in the range and abundance of the Chorister Robin-Chat (Cossypha dichroa) - an endemic forest specialist that is reported to move seasonally between high-altitude forest patches where they breed in summer, and lowland coastal forests where they overwinter. Beyond diet, body morphology and vocalisations, much of the information available on the altitudinal movements of C. dichroa is based on secondary sources and the assumptions therein. This study aimed to investigate the potential utilisation of δ13C and δ15N stable isotopes in determining the dietary niche width and altitudinal movements of C. dichroa. Feathers obtained in forested patches of the Limpopo, KwaZulu-Natal and Eastern Cape provinces exhibited a wide trophic niche width and generalised diet. Strong regional separation is apparent in the isotopic signatures suggesting little movement between provinces. A comparison of 13C-isotopes showed minimal variation that point to a uniformity in the carbon-base utilised by C. dichroa across their range. The 15N-signatures obtained in Limpopo, however, revealed a distinct trophic segregation between the northern-most Chorister populations and their southern counterparts. No altitudinal movements were detected in the isotopic signatures of recaptured Choristers, but more research is needed to investigate the long-term accuracy of these results and the breeding potential of resident Choristers in lowland coastal forests; especially when considering the reduced range and abundance reported for this endemic species.

Obesity is widely considered a primary risk factor for type 2 diabetes (T2D). However, less is known about the early adaptive responses to short-term periods of high-fat energy excess (HFEE). Previous reports detailing whole-body adaptation to fat and energy oversupply are equivocal, perhaps, in part, owing to use of different experimental protocols, varying durations of dietary manipulation and participant cohorts with individuals of varying characteristics. In addition to use of different dietary protocols between studies, alterations in functional end-point measures due to the type of dietary fat consumed warrants consideration. Daily n-3 PUFA intake, commonly obtained from pelagic fish oil (FO) consumption, has been shown to positively associate with insulin sensitivity in epidemiological studies and thus may be a useful dietary strategy for slowing insulin resistance development. Chapter 2 of this thesis extends previous literature by demonstrating that 6 d HFEE (150 % habitual energy intake; 60 % of energy from fat) does not clearly alter whole- body insulin sensitivity, irrespective of FO consumption. However, investigation of metabolism at the tissue level, as presented in Chapter 3 of this thesis, offers insight into a potential tissue-specific level of regulation that precedes whole-body regulation. Skeletal muscle insulin signalling protein (e.g. protein kinase B (PKB)) activity, levels of certain ceramide species, and AMPK α2 activity were altered following HFEE and may explain the early maladaptive responses to short-term HFEE. Moreover, FO intake as 10 % of total fats mediated some of these molecular responses, including PKB and AMPK α2 activity, reflecting possible functional effects of FO at the subcellular level. Regulation of these metabolic / molecular responses at both the tissue and whole- body level can be explained, in part, by genetic predisposition, environmental influence and more recently epigenetics, including microRNAs (miRNAs). In Chapter 4, we characterised the plasma and skeletal muscle miRNA responses to HFEE and oral glucose ingestion. We demonstrate transient changes in levels of certain miRNAs following oral glucose ingestion in both tissue types and in response to HFEE in skeletal muscle. However, no significant correlations between basal plasma and skeletal muscle miRNA levels were observed, suggesting that our candidate plasma miRNAs may be co-ordinating functional changes in other tissue types. Plasma miR- 145-5p and skeletal muscle miR-204-5p predicted a significant proportion of the variance in mean whole-body insulin sensitivity change in response to HFEE. These data indicate that these miRNAs may be useful biomarkers of insulin resistance development following HFEE. A constraint of this thesis is that all conclusions are made within the context of statistically unaltered insulin sensitivity. Therefore, future investigations of diet-induced maladaptation should consider establishing a time course of insulin resistance development in response to HFEE, or use different study populations. Populations that are more susceptible to T2D development, e.g., overweight, sedentary individuals would be of particular interest. These data would aid development of a working model of diet-induced insulin resistance that has more direct application to T2D progression and extends the data presented herein.

Les zones côtières du monde entier sont sous fort pression de contamination anthropique comme conséquence de la concentration de la plupart de la population mondiale et des activités économiques le long des côtes et des estuaires. La menace de contaminant sur les écosystèmes rend primordial le développement d'outils capable de détecter les modifications biogéochimiques en vue d'aider dans la prévention, la gestion, et la prédiction de risques dans les études environnementales. Dans ce but, cette thèse étudie la biogéochimie des isotopes du Zinc (Zn) en vue de développer un outil capable de tracer les sources naturelles et anthropiques, d'identifier les processus biogéochimiques et de permettre à la biosurveillance de la contamination par les métaux dans les zones côtières et les mangroves. A cette fin, les compositions isotopiques du Zn ont été déterminées à plusieurs échantillons naturels prélevés dans la baie de Sepetiba (au sud-est du Brésil), un estuaire lagunaire affecté par une côte industrialisée située près de Rio de Janeiro. Cette baie constitue un laboratoire naturel idéal pour valider le système isotopique du Zn. En effet, cette zone héberge des écosystèmes d'intérêt commercial et écologique -estuaire, mangrove, estran- menacés par la contamination d'une ancienne activité de galvanoplastie, et d'autres sources diffuses. Les échantillons collectés comprennent des carottes de sédiments, des sédiments de la superficie des mangroves, des matériaux particulaires en suspension (SPM), des feuilles provenant d'arbres de mangrove, des tissus de mollusques bivalves (huîtres et moules) et des roches. Minéraux de dépôt de Vazante (Brésil) ont été collecté pour representé matière première utilisée par l'industrie de la galvanoplastie. Tout d'abord, un travail initial de laboratoire a établi une méthode exacte et précise pour les déterminations isotopiques Zn en échantillons naturelles par spectrométrie de masse avec plasma couplé par induction et multicollecteur (MC-ICP-MS). Des analyses spatiales et temporelles des compositions isotopiques du Zn des échantillons de sédiments et de roches s'ajustent bien à un modèle de mélange entre trois principales extrémités : i) les matériaux continentaux charriés par les rivières ; ii) les sources marines ; et iii) une source anthropique majeure associée aux anciens déchets de galvanoplastie jetés dans la baie. Les carottes de sédiment collectées dans la vasière ont montré une haute corrélation entre la composition isotopique du Zn et le facteur d'enrichissement du Zn. Ceci suggère : i) une bonne préservation du registre isotopique des sources naturelle et anthropique, ii) l'absence de fractionnement isotopique significatif durant le transport de sédiments ou durant les réactions diagénétiques pos-dépositions dans le système estuarien
Coastal areas worldwide are under strong pressure from anthropogenic contamination, as most of the global population and of economic activities are concentrated along the coasts and estuaries. The threaten of contaminant releasing into these ecosystems makes imperative the development of tools capable of detecting biogeochemical changes in order to help prevention, monitoring and prediction of risks in environmental studies. In this way, this thesis investigates the isotope biogeochemistry of Zinc (Zn) in order to develop a tool capable of tracing natural and anthropogenic sources, identifying biogeochemical processes and enabling the biomonitoring of metal contamination in coastal areas and mangroves. To this end, Zn isotopes compositions were determined in several natural samples collected from Sepetiba bay (southeastern Brazil), an estuarine-lagoon impacted by an industrialized coastal area near Rio de Janeiro. This bay constitutes an ideal natural laboratory for evaluating the Zn isotopic system to environmental issues, since it hosts important ecosystems of commercial and ecological interest - estuaries, mangroves and tidal flats - threaten by the metal contamination resultant of old electroplating activity and other anthropogenic diffuse sources. The collected samples include sediment cores, surface mangrove sediments, suspended particulate matter (SPM), leaves of mangrove's trees, tissues of bivalve mollusks (oysters and mussels) and rocks. Ores from Vazante deposit, Brazil were collected to represent the raw material used in the old electroplating industry. Firstly, an initial laboratory work established a method for accurate and precise determinations of Zn isotope compositions in natural samples by multi-collector inductively coupled plasma-mass spectrometry (MC-ICP-MS). Spatial and temporal analysis of Zn isotope compositions of sediment and rock samples fits well in a model of mixing between three main end-members: i) continental materials brought via rivers; ii) marine sources; and iii) a major anthropogenic source associated to the old electroplating wastes released into the bay. Sediment cores collected in the mud flat showed high correlation between Zn isotope compositions and Zn enrichment factors, suggesting (i) good preservation of isotopic records of natural and anthropogenic sources and (ii) no significant isotopic fractionation during sediment transport or as a result of diagenetic reactions post-deposition in the estuarine system. The sediment core sampled from a mangrove located in the zone impacted by the old electroplating activity presented levels of Zn up to 4% (dry weight) and preserved the isotopic signatures of electroplating wastes. However, there is evidence that biogeochemical processes triggered by hydrodynamics, bioturbation or rhizosphere processes slightly changed the isotopic signatures in some layers. Calculations based in this mixing model quantified contributions of the major anthropogenic source of Zn, ranging from negligible values in the pre-industrial period to nearly 80% during periods of electroplating activities between the 60's and 90's

Stable water isotopes (H2O, H18O, and HDO) are incorporated into the microphysics schemes of two different atmospheric models. This thesis describes the use of these molecules as tracers in precipitation budgets to assess the processes controlling the isotopic signatures of precipitation in the tropics and orographic snow in the mid-latitudes. The idealized simulations of seasonal precipitation budgets in the tropics determine that increased vapor convergence during intense precipitation is most important for setting the isotopic composition of the convective precipitation. The isotopic signal of the converged vapor is more important than the local evaporation and smaller scale post-condensational processes. Flow over a 2D-mountain and realistic simulations of orographic clouds show that the isotopic signature of precipitation is more sensitive to changes in mountain height and initial temperature profiles than to the cloud droplet number concentration. Riming of cloud liquid and vapor deposition onto ice are the largest source terms for orographic precipitation, and have distinct isotopic signatures that are altitude-dependent. When riming is the larger source term, precipitation tends to be more enriched than when vapor deposition dominates.
Earth and Planetary Sciences

Delineating spatial patterns of precipitation isotopes (“isoscapes”) is important for studies including the hydrology of terrestrial systems, present and past interpretations of climate, and tracer-aided hydrological modelling, among others. However, the extent to which precipitation isoscapes can be predicted across Canada has not been fully articulated. This thesis combines isotopes in precipitation (δ18Oppt) observations from two regional and one global network to create long term and time series precipitation isoscapes for Canada and the northern United States. Multi-linear regressions of a small suite of geographic and climate variables generate the best performing long-term and seasonal models of δ18Oppt. These models are used to develop long term isoscapes for Canada, which capture the general spatial and seasonal trends in δ18Oppt, showing an improvement upon results from previous studies using global models. Building upon long-term δ18Oppt prediction, δ18Oppt observations alongside climatological and geographic predictors are used to create empirical time series prediction models. Five regionalization approaches are used to separate the study domain into isotope zones to explore the effect of spatial grouping on simulations. Generally, the models capture the timing and magnitude of intra-annual (seasonal) δ18Oppt cycles across the study domain while simulating moderate inter-annual variation; however often fail to capture the anomalies in observed δ18Oppt. Uncertainty in predictions is quantified spatially and temporally, and the Köppen-Geiger (Kpn) regionalization is selected as the preferred regionalization scheme for future applications due to adequate model performance and lack of border issues at regional boundaries. Finally, estimates of monthly δ18Oppt from Kpn models, long term annual averages, and daily REMOiso output are used to force an isotope-enabled hydrological model, isoWATFLOOD, in the Fort Simpson Basin, NWT, Canada. Results show streamflow simulations are not significantly impacted by choice of δ18Oppt input; however, oxygen-18 in streamflow and the internal apportionment of water (and model parameterizations) are impacted, particularly during large precipitation and snowmelt events. This work shows how isoWATFLOOD can be used in regions with limited δ18Oppt observations, and that the model can be of value in such regions. This study reinforces that a tracer-aided modelling approach works towards diagnosing issues surrounding model equifinality.
February 2017

Ce doctorat repose sur l'utilisation de Glycymeris glycymeris, un bivalve de la famille des Glycymerididae, pour reconstruire la variabilité environnementale en rade de Brest (France). Il vise à comparer des données géochimiques archivées dans ces coquilles avec diverses variables biologiques et écologiques. Les objectifs sont d'identifier de potentiels proxys et d'étendre notre connaissance de la variabilité environnementale avant les premières mesures instrumentales.Au total, 38 spécimens (vivants ou morts) ont été utilisés pour construire une chronologie s'étendant de 1891 à 2014.Les indices de croissance standardisés suggèrent que la croissance coquillière est principalement influencée par le débit de l'Elorn, la salinité et la matière particulaire en suspension.Des analyses isotopiques, réalisées sur les portions juvéniles de 24 spécimens, mettent en évidence que les variations de δ18Oaragonite enregistrent fidèlement la température de surface, permettant sa reconstruction sur 45 ans en rade de Brest. En terme de forçage climatique, ces variations de température en rade semblent contrôlées par le gyre subpolaire et l'East Atlantic Pattern.Cinq coquilles (3 d'âge inférieur à 10 ans et 2 âgées de 45 ans) ont ensuite été analysées pour leurs concentrations en strontium et magnésium par LA-ICP-MSLes concentrations en Mg et Sr, quant à elles, sont positivement corrélées à la température de l'eau à une échelle sub-annuelle, mais négativement à l'échelle annuelle.Cette étude met en lumière le potentiel de G. glycymeris comme archive de la variabilité climatique et environnementale en rade de Brest. Du fait du nombre important de spécimens sub-fossiles en rade, cette thèse fournit une base de travail pour l'extension de ces reconstructions dans un passé encore plus lointain
This PhD thesis uses Glycymeris glycymeris, a temperate bivalve in the Glycymerididae family, to reconstruct environmental variability in the Bay of Brest, France. This work comprises of geochemical data archived within shells, compared with several biological and ecological variables. The aims of this study were to assess for potential proxies and expand environmental knowledge prior to local observational records.Thirty-eight live- and dead-collected specimens were used to create a chronology spanning 1891 to 2014. When the standardised growth index was correlated with local environmental factors, it showed that the predominant drivers of growth were Elorn inflow, salinity and suspended particulate matter.Isotopic analysis was undertaken on the juvenile increments of 24 shells. Our results highlight that variations in δ18Oaragonite accurately record local sea surface temperatures, leading to the creation of a 45-year SST reconstruction for the Bay of Brest. Correlations between this and climate forcings show that SSTs in this area are controlled by the subpolar gyre and the East Atlantic Pattern.Five shells (three under the age of 10 and two aged 45) were analysed using a LA-ICP-MS to determine the quantity of strontium and magnesium. Mg and Sr intensities are positively correlated with temperature sub-annually, but on an annual scale there is a negative correlation.This study conveys the potential of G. glycymeris as an archive of climatic and environmental variability in the Bay of Brest. As there are a large number of sub-fossil specimens in the area, this study also provides an anchored base for expansion further back in time

The Arctic acts as both an indicator and a facilitator of global climate change. Many studies have identified the manifold changes in the Arctic hydrological system resulting from global warming. These changes have affected the freshwater balance of the northern North Atlantic and therefore pose a problem to deep water formation in this region, further impacting the global climate. This thesis uses the quasi-conservative properties of oxygen and hydrogen isotopes in watermasses to identify and quantify the freshwater sources to the ocean currents exiting the Arctic into the northern North Atlantic. Comparison of historical oxygen isotope data from the East Greenland Current system with data presented here indicates that its freshwater isotope signature has not been temporally constant. Specifically, in 2005, there was a shift to a value ? 10 h heavier than the long-term mean, indicating a large increase in sea ice meltwater admixture that coincides with a large, short-term peak in the Fram Strait sea ice export. Therefore, interannual variations in the sea ice export are transported to the watermasses downstream. Oxygen isotope data from the West Greenland Current confirm that the freshwater signal in the East Greenland Current system is transferred around the tip of Greenland. However, there is an apparent decrease in the freshwater concentration in the West Greenland Current relative to the east. This potentially corroborates the previously reported retroflection of part of the East Greenland Current into the North Atlantic subpolar gyre. The primary freshwater sources to the Labrador Current are identified as Arctic surface waters exported via the Canadian Archipelago, Hudson Strait and the West Greenland Current. There is also considerable sea ice formation and melt influence on the Labrador Shelf. The world surface ocean oxygen and hydrogen isotope mixing relationship is observed to be regionally and seasonally robust, with the exception of areas with a high meteoric water influence. The use of hydrogen isotopes as a tracer for Greenland glacial meltwater in the East Greenland Current system is investigated and the preliminary results are positive although further work is necessary to establish the value of this tracer. This thesis highlights the importance of stable isotope studies for identifying and quantifying the freshwater in the currents exiting the Arctic, allowing the key pathways of Arctic freshwater into regions of deep water formation in the North Atlantic to be identified and monitored. These pathways are: the East Greenland Current into the Nordic Seas and the North Atlantic subpolar gyre; the West Greenland Current into Labrador Sea; and the Labrador Current into the general North Atlantic circulation.

L’Hémisphère Sud, et plus précisément le sud de l’Amérique du Sud, sont très sous-représentés dans les reconstitutions climatiques globales du fait d’un manque de données paléoclimatiques robustes. Mes travaux de thèse ont donc porté sur l’évaluation de l’archive naturelle cernes d’arbre, abondante le long de la Cordillère des Andes, comme traceur paléoclimatique. Je me suis ainsi appliquée à étudier la réponse régionale de deux espèces d’arbre (Fitzroya cupressoides et Nothofagus pumilio) natives du nord de la Patagonie (41°S, Argentine) aux forçages climatiques externes en analysant leurs différents paramètres physiques. Pour cela, j’ai commencé par déterminer l’influence du climat local et de grande échelle sur leur croissance en étudiant les variations temporelles de leurs largeurs de cerne, puis j’ai essayé d’extraire le signal climatique enregistré dans la composition isotopique de l’oxygène et du carbone de la cellulose de ces cernes. Deux résultats majeurs de ma thèse ont émergé: j’ai mis en évidence (1) des réponses non-linéaires de la croissance au cours du temps liées aux changements de régimes climatiques et, (2) le fort potentiel du delta18O et delta13C de la cellulose pour enregistrer les variations de température d’été-automne sur une large région aux latitudes moyennes de l’Amérique du Sud (35°-55°S). Du fait des relations fortes qui les lient aux températures, les outils isotopiques peuvent être utilisés pour reconstituer des chronologies de température mais aussi des modes climatiques tels que l’Oscillation Antarctique
The Southern Hemisphere, and particularly southern South America, are very under-represented in global climate reconstructions due to a lack of robust paleoclimatic data. My thesis was therefore focused on the evaluation of the tree-ring archive, which is widespread along the Andes, as a paleoclimatic tracer. I studied the regional response to external climate forcing of two native species (Fitzroya cupressoides and Nothofagus pumilio) in northern Patagonia (41°S, Argentina), by analysing their different physical tree-ring parameters. In this perspective, I analysed the temporal variations of the width and of the oxygen and carbon isotopic compositions of the cellulose of their rings and related them to local and large-scale climate variations. Two major results of my thesis have emerged: I highlighted (1) non-linear growth responses over time related to shifts in climate regimes and, (2) the potential of cellulose delta18O and delta13C to record summer-autumn temperature variations over a large area in the mid latitudes of South America (35°-55°S). As their variations are strongly linked to temperature the isotopic tools can be used to reconstruct chronologies of temperature but also of climate modes such as the Southern Annular Mode

Tesis para optar al grado de Magíster en Ciencias, Mención Geología
El presente trabajo se centra en el uso de isótopos estables y trazadores antropogénicos para investigar el origen, los tiempos de residencia y la evolución de las aguas termales en el Complejo Volcánico Lonquimay-Tolhuaca, ubicado en la parte central de la Zona Volcánica Sur. Veinte muestras de agua subterránea, surgiendo en un amplio rango de temperaturas (8-96°C), son analizadas para determinar su composición química, incluyendo elementos mayores, razones isotópicas (δ2H, δ18O, δ13CTDIC) y la concentración de clorofluorocarbonos (CFCs) y hexafluoruro de azufre (SF6) disueltos. Adicionalmente, se presenta un compilado de toda la información disponible sobre la composición isotópica de la precipitación en la región de la Araucanía. Mediante un modelo de fraccionamiento de Rayleigh aplicado a los isótopos de oxígeno, se logra constreñir la elevación a la cual se produce la recarga del sistema. Los valores de δ13CTDIC en las aguas indican la adición de CO2 del suelo a una fuente de origen atmosférico en la mayoría de las muestras. No obstante, procesos de ebullición y desgasificación magmática se evidencian en las surgencias termales ubicadas en los flancos de volcanes. La composición isotópica de las aguas termales, una vez calentadas en profundidad, es modificada posteriormente por procesos de desgasificación de CO2 y precipitación de carbonatos durante su ascenso. Todas las muestras de aguas termales presentan concentraciones bajas pero detectables de CFC-11, CFC-12, CFC-113 y SF6, lo que sugiere la adición de una pequeña fracción (2 a 22%) de agua meteórica moderna al sistema. La temperatura de surgencia de las aguas termales en el Complejo Volcánico Lonquimay-Tolhuaca se relaciona directamente con la distribución de edad en las muestras. Estas diferencias en los tiempos de residencia se atribuyen a los distintos mecanismos de circulación de cada tipo de agua: por un lado, las aguas frías poseen tiempos de residencia cortos y evidencian una circulación somera a través de un medio poroso, mientras que las aguas termales poseen tiempos de residencia mayores y evidencian un flujo canalizado a través de zonas de falla. El flujo de las aguas termales a través de estos conductos de alta permeabilidad vertical impide que sean diluidas con agua meteórica durante el ascenso. Los datos de este estudio confirman que las redes de fallas y fracturas con distintas orientaciones ejercen un control sobre los tiempos de residencia, el ascenso y las tasas de mezcla de distintos fluidos en este segmento de la Cordillera de los Andes, determinando así su composición química e isotópica. Asimismo, nuestros resultados muestran que el análisis geoquímico e isotópico convencional, en conjunto con el uso de trazadores ambientales (incluyendo los trazadores antropogénicos, CFC y SF6) son una poderosa herramienta para entender la dinámica hídrica de los sistemas geotermales.
Centro de Excelencia en Geotermia de los Andes (CEGA), proyecto FONDAP-CONICYT 15090013, y por el Núcleo Milenio Trazadores de Metales NC130065

In this thesis, I have developed a new methodology for the accurate determination of mass-dependent variations in nickel (Ni) isotope compositions. Nickel is initially separated in a three-column ion-exchange procedure, and the purified solutions are analysed by multi-collector inductively coupled plasma mass spectrometry (MCICPMS) using a double-spike technique. Using this methodology, I have measured the first Ni isotope ratios for a wide variety of natural geological samples. Significant Ni isotope variations were observed, with an overall spread in delta 60Ni-values of -0.9 to 2.5 permil. In igneous rocks Ni isotopes appear to be largely homogeneous, with only small variations (0.2 permil) between different rock types. Weathering of silicate rocks does on the other hand appear to cause significant fractionation of Ni isotopes, probably producing an isotopically heavy riverine input to the ocean. A heavy isotope signature is also visible in hydrogenetic ferromanganese crusts, with surface scrapings from globally distributed crusts show an average delta 60Ni-value of 1.65 permil. However, the variation in these samples is over 1.5 permil, likely reflecting local sources or biological processes, or alternatively indicating a heterogeneous Ni isotopic composition of the ocean. Organic-rich sediments also show heavy isotopic compositions, which are possibly transferred to the crude oils originating in these types of sediments. The only significant reservoir of light Ni isotopes found during this project are sulphides from magmatic systems. Overall, this thesis demonstrates the potential of this system as a powerful new tracer for a variety of geochemical processes.

Les changements paléoenvironnementaux se produisant pendant le Sarmatien dans la Paratéthys Centrale ont été reconstitués par l'étude des foraminifères (36 espèces) et des ostracodes (28 espèces) de deux forages, combinée à une analyse géochimique de leurs squelettes calcitiques, des coquilles aragonitiques de gastéropodes et des dents phosphatiques de rongeurs.La composition de la microfaune indique que la connexion entre la Paratéthys et la Méditerranée est interrompue ou réduite à la base du Sarmatien mais qu'un bras de mer persiste entre Paratéthys Centrale et Paratéthys Orientale jusqu'à la fin du Sarmatien. Le Sarmatien inférieur est caractérisé par des eaux saumâtres peu profondes (maximum 80 m), bien ventilées, des températures stables (~ 15°C), un riche couvert végétal (algues et/ou phanérogames) et des efflorescences phytoplanctoniques périodiques. Un événement transgressif y est observé (TST de 3ème ordre; TB 2.6 du cycle global). Les changements faunistiques qui se produisent à la limite entre Sarmatien inférieur et moyen sont expliqués par un évènement de type HST accompagné de conditions dysoxiques. A la fin du Sarmatien moyen, une baisse du niveau marin relatif d'environ 50 m se produit et des eaux tempérées chaudes, plus saumâtres (17-23‰) et bien ventilées se mettent en place. Après un court épisode régressif, une connexion est rétablie entre la Paratéthys et la Méditerranée au début du Sarmatien supérieur. Des eaux chaudes (15-21° C), bien ventilées, correspondant à des lagunes marines et des marécages avec de fortes variations de la salinité (15-43 ‰) s'installent alors avant un isolement ultime de la Paratéthys qui se produit à la fin du Sarmatien.

Regions of surface water and groundwater exchange are major sites for the transfer and transformation of solutes and nutrients between stream and subsurface environments. Conventional stream and groundwater exchange investigations are limited by methodologies that require intensive field investigations and/or the set-up of expensive infrastructure. These difficulties are exacerbated where hydraulic gradients are very low and stream discharge highly variable. This thesis uses a suite of environmental tracers (Cl-, Rn-222, H-2 & O-18, Sr-87/Sr-86) to characterise the extent of stream and groundwater exchange between a sand bed stream and adjacent alluvial aquifer in a subtropical catchment (the Wollombi Brook) of eastern Australia. The aims were to identify sources and relative contributions of different sources of groundwater to stream discharge and specifically to improve the methodology of using Rn-222 to obtain quantitative estimate of groundwater fluxes. The sensitivity of the Rn-222 technique for identifying groundwater discharge based on the Rn-222 concentration in stream water was improved via an iterative numerical approach to account for Rn-222 loss from stream water via turbulent gas exchange and radioactive decay. Optimal distances between stream sampling points for defining the magnitude of groundwater discharge to stream flow based on Rn-222 concentrations in stream water is a function of average stream velocity and water depth. The maximum allowable distance between sampling points for determining the magnitude of groundwater discharge to the Wollombi Brook was 2 km. This work showed that groundwater discharged to all reaches of the Wollombi Brook during baseflow and flood recession conditions. Alluvial groundwater contributed less than 30% of water to stream flow in the mid Wollombi Brook catchment. Dilution of steady-state Rn-222 concentrations measured in transects from the stream to the alluvial sediments showed that significant surface water and groundwater exchange occurs even when gradients between surface water and groundwater are low. Lateral stream water influx to the adjacent alluvial aquifer was more extensive in the lowland areas of the Wollombi Catchment during low flow than flood recession conditions. Extensive stream water influx to the adjacent alluvial aquifer occurs contrary to the net direction of surface water and groundwater flux (as indicated by hydraulic gradients toward the stream channel). The rate of stream and groundwater exchange within the adjacent alluvial aquifer appears to be greatest during baseflow conditions. Fresh alluvial groundwater appeared to provide a buffer against higher salinity regional groundwater discharge to the alluvial aquifer in some reaches of the Wollombi Brook catchment. Pumping of the alluvial aquifer and diversions of surface water may jeopardise the water quality and volume of the alluvial aquifer and induce water flow from the regional aquifer toward the stream, potentially salinising the fresh alluvial aquifer and subsequently the stream. The change in the Cl- concentration and the variation in slope of the deuterium � oxygen-18 line between consecutive stream sampling points could be used to differentiate between regional and alluvial groundwater discharge to stream flow. Incorporating this information with three-component end-member mixing using [Sr2+] and Sr-87/Sr-86 showed that stream and alluvial groundwater exchange within the stream channel was highest in the lowland floodplains during low flow conditions. The least stream and alluvial groundwater exchange occurred in the low streambed gradient mid reaches of the Wollombi Brook regardless of stream stage. The greatest difference in the degree of stream and alluvial groundwater exchange between high and low stream stages occurred in the lowland floodplains of the Wollombi Brook.

L’objectif de la thèse vise à déterminer les facteurs et processus qui contrôlent l’origine et la qualité des eaux souterraines alluviales et ainsi à mieux comprendre le fonctionnement et la vulnérabilité des aquifères alluviaux qui occupent une place prééminente dans le paysage hydrogéologique mondial tant pour leur rôle économique - production d'eau potable, développement agricole - que pour leur rôle écologique. Des mesures hydrodynamiques, hydrochimiques (ions majeurs, traces, molécules phytosanitaires et pharmaceutiques) combinées à des déterminations isotopiques (oxygène-18, deuterium, carbone-13) ont ainsi été effectuées sur 19 points incluant puits, piézomètres et eaux de surface, de février 2011 à novembre 2012, afin d’évaluer l’origine et la qualité de l’eau souterraine dans l’aquifère alluvial de la rivière Allier, un des principaux tributaires de la Loire. La zone d’étude, située près de la ville de Clermont-Ferrand (France), joue par ailleurs un rôle socio-économique majeur, la nappe alluviale de l’Allier constituant la principale ressource en eau potable pour une population d’environ 100 000 habitants. D’un point de vue hydrodynamique, l'eau souterraine circule généralement du sud au nord, avec une alimentation naturelle à partir des coteaux adjacents, dans la partie non-pompée de l'aquifère. Dans la zone de pompage, cette circulation naturelle est modifiée par le pompage qui fait pénétrer l’eau de la rivière Allier dans l’aquifère. La recharge de l’aquifère dépend alors de quatre pôles de mélange : pluie, rivière Allier, coteaux adjacents et partie sud, non-pompée, de l’aquifère. Les résultats chimiques et isotopiques obtenus permettent de cartographier la contribution de chaque pôle de mélange. [...] Ces résultats mettent en évidence la vulnérabilité de l’aquifère face aux pollutions. Les parties méridionale et orientale du site sont affectées par des arrivées d’eaux de qualité médiocre démontrant l’importance de la définition d’un périmètre de protection adaptée. Près de l’Allier, une attention particulière doit être portée non seulement aux pollutions ponctuelles qui peuvent se produire sur le cours de la rivière, mais également aux pollutions chroniques liées notamment aux rejets des stations d’épuration pourvoyeurs de polluants tels les molécules pharmaceutiques. Toutes les informations acquises devront être incluses dans les stratégies de gestion d'eau souterraine afin protéger la durabilité de cette ressource de valeur. Les résultats s’appuient sur les investigations menées sur la nappe alluviale de l’Allier, néanmoins la méthodologie utilisée et sa transposition à des systèmes analogues est l’une des perspectives majeures de cette étude
Hydrodynamic, hydrochemical (major ions, traces, pharmaceuticals and pesticides), and isotopic investigations (oxygen-18 and deuterium) were carried out on 19 points, including boreholes, piezometer, surface water, and springs from February 2011 to November 2012, to assess groundwater quality in the unconfined shallow alluvial aquifer of the Allier River (one of the main tributary of the Loire River). The study area, located near the city of Clermont-Ferrand (France), plays an important socio-economic role as the alluvial aquifer is the major source of drinking water for about 100 000 inhabitants. The objective of the project aims at understanding the functioning and the vulnerability of alluvial aquifers that occupy a pre-eminent position in the hydrogeologic landscape both for their economic role - production of drinking water and agricultural development - and for their ecological role. Moreover, this study also targets at determining the factors and processes controlling shallow groundwater quality and origin. The water circulates from the south, with a natural alimentation from the hills in the non-pumped part of the alluvial aquifer. In the pumping zone, this general behaviour is altered by the pumping that makes the water from the Allier River enter the system in a large proportion. Four end-members have been identified for the recharge of the alluvial groundwater: rainfall, Allier River, surrounding hills’ aquifer and the southern non-pumped part of the alluvial system. Results indicate that, despite the global Ca-HCO3 water type of the groundwater, spatial variations of physico-chemical parameters do exist in the study area. Ionic concentrations increase from the Allier River towards east due either to the increase in the residence time or a mixing with groundwater coming from the aquifer’s borders. Stable isotopes of the water molecule show the same results: boreholes close to the river bank are recharged by the Allier River (depleted values), while boreholes far from the river exhibit isotopic contents close to the values of hills’ spring or to the southern part of the alluvial aquifer, both recharged by local precipitation. One borehole (B65) does not follow this scheme of functioning and presents values attesting of a probable sealing of the Allier River banks. Based on these results, the contribution of each end-member has been calculated and the functioning of the alluvial system determined. According to this general scheme of functioning, origins of pollution (agricultural, urban) have been determined and clues to the protection of such hydrosystems defined

Gas chromatography mass spectrometry (GCMS) and inductively coupled plasma mass spectrometry (ICPMS) were evaluated for the measurement of selenium (Se) and Se stable isotope ratios. GCMS and ICPMS were found to be accurate for quantitative Se analysis in biological matrices by isotope dilution using Se-78 and Se-76 as internal standards, respectively. A higher precision was obtained for ICPMS than GCMS enabling a smaller quantity of the tracer to be administered to subjects in labelling experiments. The isotopes of choice for metabolic tracers were Se-76 when sample analysis was by GCMS and Se-77 and Se-82 when analysis was by ICPMS. The influence of copper (Cu) on endogenous fecal Se excretion and true absorption of Se in nonlactating Holstein cows was examined by the use of Se stable isotopes as tracers. The method involved the application of conventional balance techniques in conjunction with isotopic enrichment of the body Se pools. Selenium in several tissues following oral and intravenous routes of isotope administration were evaluated as the precursors of endogenous fecal Se. Two cows fed a Se deficient diet (0.035 mg kg⁻¹) were administered 4 mg Se-76 orally, daily, for 5 d. After a 10-d equilibration period total collection of feces was made daily for two 5-d periods. The animals were then sacrificed and samples obtained from all major tissues and fluids. Se-7 6 enrichment (tracer/tracee mass percent, TTMP) in tissues was variable (< 0.56 - 13.4). However, enrichment was similar (9.8 - 12.9) in the tissues considered as potential contributors to endogenous fecal Se (serum, epithelium of the stomach, liver, bile, pancreas, small intestine and colon). Enrichment in serum and liver was used to calculate endogenous fecal Se. Apparent absorption of Se in the two cows was negative (-37 and -147 µg d⁻¹). Correction of apparent absorption for the fecal Se of endogenous origin gave a true Se absorption (% of intake) of 10 and 16%. The percentage of total fecal Se of endogenous origin was 23 and 36%. In two trials, 5 or 6 cows were assigned to one of two Cu-supplemented treatment diets: 0 mg kg⁻¹ or 17 mg kg⁻¹. The basal diet contained 0.19 mg Se kg⁻¹ and 13 mg Cu kg⁻¹. To each cow ~4.6 mg Se-77 and ~1.3 mg Se-82 were administered by oral and intravenous routes, respectively. After a 14-d equilibration period, total collection of feces and urine were made daily for two 5-d periods. Serum was collected on the first, third and fifth days of each period. Liver biopsies were taken 2 d following the completion of the balance periods. The estimates of endogenous fecal Se ( d⁻¹) from enrichment in the serum (256) and liver (235) following oral administration of the tracer and from enrichment in serum (241) following intravenous administration were not significantly different (P>0.05) but were higher than the estimate from the enrichment in liver (197) (P<0.05). No significant differences (P>0.05) were present when true absorption ( µg d⁻¹) was determined from enrichment in serum (290) or liver (268) following oral administration or from enrichment in serum (274) or liver (230) following intravenous administration. It was concluded the analysis of serum or liver with oral administration or the analysis of serum with intravenous administration of the tracer would provide reliable methods for estimation of endogenous fecal Se and true absorption. There was no effect of Cu on endogenous fecal Se excretion or true absorption of Se. Apparent and true absorption were 3.2 and 11%, respectively. Approximately 90% of the total Se excreted was in the feces, of which, 9.7% was of endogenous origin. The use of Se stable isotopes as metabolic tracers in dairy cattle provided a safe alternative to the use of radioactive tracers and enabled experiments requiring multi-isotopic enrichment to be performed.
Land and Food Systems, Faculty of
Graduate

L’étude de l’écologie alimentaire d’une espèce est une clé de la compréhension de sa biologie et de son fonctionnement dans l’écosystème. Ainsi, les interactions proies-prédateurs sont une des voies qui structurent et déterminent les dynamiques des populations et le réseau trophique à l’échelle d’un écosystème. Parmi les sites d’étude d’intérêt majeur, le milieu marin est un espace soumis à des forçages naturels et anthropiques. A l’échelle de l’Océan Atlantique Nord-Est, le Golfe de Gascogne est une vaste baie bordée par l’Espagne au sud et la France à l’est. Ce Golfe est le siège historique d’une intense activité de pêches commerciales pour lesquelles les principales espèces de petits poissons pélagiques ciblés sont la sardine, Sardina pilchardus, et l’anchois, Engraulis encrasicolus. L’objectif de ces travaux est d’analyser l’écologie alimentaire printanière, de ces deux petits poissons pélagiques dans le Golfe de Gascogne. Pour ce faire, le premier volet s’est focalisé sur le compartiment des proies mésozooplanctoniques via deux approches : la caractérisation de leurs dynamiques spatio-temporelles sur la décennie 2003-2013 et la mesure de leur contenu énergétique au printemps. Il apparaît, à cette saison, que tous les types de proies ne se valent pas énergétiquement et que notre site d’étude représente une mosaïque d’habitats alimentaires. De plus, la communauté mésozooplanctonique printanière présente une forte structuration spatiale, une évolution temporelle marquée par un changement majeur d’abondance et un contrôle par la biomasse de microphytoplancton. Le second volet de ces travaux est relatif à une approche méthodologique de l’analyse de l’écologie alimentaire de S. pilchardus et E. encrasicolus. Trois traceurs trophiques distincts ont été utilisés : les ratios isotopiques du carbone et de l’azote, la faune parasitaire et les niveaux de contamination en mercure. Pour perfectionner l’utilisation du premier de ces traceurs, une approche expérimentale a été menée sur S. pilchardus pour déterminer un facteur de discrimination trophique. Finalement, il apparaît que l’utilisation de ces trois traceurs a toujours permis de mettre en évidence une variabilité temporelle relative de l’écologie alimentaire des poissons étudiés. En revanche, aucune dynamique spatiale n’a pu être détectée via ces traceurs
Dietary studies of marine species constitute an important key to improve the understanding of its biology and of its role in the ecosystem. Thus, prey-predator relationships structure and determine population dynamics and the trophic network at the ecosystem scale. Among the major study sites, the marine ecosystem is submitted to natural and anthropogenic constraints. In the North-Eastern part of the Atlantic Ocean, the Bay of Biscay is a large open area surrounded South by Spain and East by France. This bay is an historic place of intense fishery activities for which the main small pelagic species targeted are the pilchard, Sardina pilchardus and the anchovy, Engraulis encrasicolus. The aim of this work is to analyze the trophic ecology of these two small pelagic fish in spring in the Bay of Biscay. To do this, a first section is devoted to their prey composed by the mesozooplanktonic compartment, through a two-fold approach: the characterization of their spatio-temporal dynamics during the decade 2003-2013 and the measurement of their energetic content in spring. For this season, it appears that all prey types are not worth energetically and that the Bay of Biscay represents a mosaic of dietary habitat. Moreover, the spring mesozooplankton community presents a strong spatial structuration, a temporal evolution marked by a major change in abundance and a control by the microphytoplankton biomass. The second section of this work is relative to a methodological approach of the trophic ecology of S. pilchardus and E. encrasicolus. Three different trophic tracers have been used: isotopic ratios of carbon and nitrogen, parasitological fauna and mercury contamination levels. To improve the use of the first of these trophic tracers, an experimental approach has been conducted with S. pilchardus to determine a trophic discrimination factor. Finally, it appears that the use of these three trophic tracers has always been permitted to highlight a temporal variability of the relative trophic ecology of these fish. However, no spatial dynamics could be identified through these three trophic tracers

Includes bibliographical references.
Despite the importance of movement ecology studies, the field faces a prevailing challenge of methodological limitations in tracking individual organisms. This research investigated the utility of the stable isotope technique to trace movements of ducks in southern Africa. I sampled and analysed feathers of ten duck species for stable isotope proportions of Carbon (δ13C), Nitrogen (δ15N) and Hydrogen (δD), from five wetlands (Strandfontein and Barberspan in South Africa, the Manyame catchment in Zimbabwe, Lake Chuali in Mozambique, and Lake Ngami in Botswana) as test cases.Sampling was carried out at different seasons to account for seasonal isotope signature variations. Isotope signatures of feathers grown at different moulting locations were compared to test whether southern Africa shows stable isotope spatial patterns (distinct isotopic regions). Feathers grown at different life-phases were compared to test whether different sites had been used and if more mobile species showed more and stronger isotope distinctions. Finally, growing flight feathers grown at moulting locations were compared across species to query how much information on diet and foraging behaviour can be inferred from southern African duck feather stable isotopes.Feather isotope signatures were distinct by site in at least one of the tested isotopes, for the majority of ducks tested. Strandfontein had more and stronger distinctions of isotope signatures between feathers grown at different life phases. This site is the closest to the sea and most likely to have marine-influenced isotope signatures especially in δ15N, it falls within the Mediterranean climatic conditions experiencing winter rainfall unlike all the other sites. Vegetation compositions (C3 and C4 plant distributions) therefore vary across sites influencing δ13C patterns. More mobile species (only Egyptian Goose Alopochen aegyptiacus from Strandfontein, and Cape Shoveler Anas smithii from Barberspan; determined by mobility scores from other studies) had more and stronger distinctions between flight and body feathers. All the other species did not comply with mobility scores. They showed weaker and fewer tissue signature distinctions than their mobility scores suggested. There were high isotopic signature overlaps in δ13C and δ15N across and within feeding guilds at each moulting site implying dietary overlaps during moulting. More overlaps occurred during the dry seasons (summer in Strandfontein and winter in Lake Chuali, Manyame catchment site, and Lake Ngami). Higher isotopic variances (higher dietary flexibility) were associated with isotope signature divergence to mobility scores especially in Cape Teals and Yellow-billed Ducks.The isotope technique is flawed with uncontrollable sources of variation which potentially confound movement inferences. It is best used when accompanied by conventional methods to detect and counter against species specific biology and dietary behaviour imposed biases in tissue isotope signatures. Further research on how species specific biological processes affect the reflection of spatial patterns of isotopes in feathers is recommended. Multi-isotope time explicit approaches and trace element analysis were also recommended. Scientists should be wary about basing management strategies or building theory about movement patterns of species based on the technique at least in stochastic environments such as southern Africa. My results provide empirical evidence that the technique is unreliable at this scale of analysis. In particular, the majority of ducks in this region are not good candidates for use of isotopic signatures in distinguishing movement patterns of southern African ducks.4983

Nitrogen (N) leaching is one of the important pathways that leads to water pollution, and previous studies have highlighted the difficulty in measuring it. The purpose of this study was to evaluate different techniques used to quantify nitrate-N (NO3-N) leaching load and determine fertiliser N use efficiency (FNUE). Lysimeter and field trial sites were planted with wheat (Triticum aestivum) (PAN3400 cultivar) at the University of Pretoria Experimental Farm, Hatfield, Pretoria. Two weighing lysimeters and a drain gauge were installed at the lysimeter trial site. Water content sensors and suction cups (SCs) were installed at 0.15, 0.3, 0.5 and 0.7 m depths in the weighing lysimeters and close to the drain gauge, while SCs, wetting front detectors (WFDs) and water content sensors were installed at 0.25 and 0.5 m in the field trial site. The crop was fertilised with 200 kg N ha-1 at both sites, but no fertiliser was applied on unfertilised control plots at the field trial site. High density drip irrigation was used at both sites, and bromide (Br-) was applied to all field plots at 0.020 kg m-2. Water was sampled from the SCs, WFDs and the bottom of weighing lysimeters and drain gauge to determine soil water NO3-N and Br- concentrations. Soil samples collected before and after the trial, and plant samples taken at tillering, flowering and physiological maturity were analysed for plant N% and stable 15N natural abundance using a mass spectrometer. Phenological and growth data from the lysimeter trial were used to calibrate Agricultural Production Systems sIMulator (APSIM) model for the first time (according to our knowledge) on wheat in South Africa. The model was then validated using data from the field trial. The drain gauge drained more frequently and in greater amounts than the weighing lysimeters, and NO3- was observed in drainage water from the drain gauge, but was undetectable from the weighing lysimeters drainage possibly because of saturated bottom layer that promoted denitrification. Based on stable 15N natural abundance, the FNUE was 68%, so the fertilised crop did not use 32% of the applied fertiliser. Good correlation was noted between the flag leaf and total plant N% at physiological maturity, indicating that flag leaf can be used to determine the FNUE without requiring whole plant analysis. The potential NO3-N leaching determined using a Br- conservative tracer was 51.5 kg ha-1 season-1. In fertilised plots, the calibrated model predicted NO3-N leaching of 22.7 kg ha-1 season-1, which was slightly lower than the drain gauge measured NO3-N leaching 24.9 kg ha-1 season. Therefore, the drain gauge shows excellent promise in quantifying N leaching but will require further testing under a range of cropping systems. Since the measured drain gauge and simulated NO3-N leaching agreed, and variables such as grain yield, total above dry matter, leaf area index and soil water content were reasonably simulated, the APSIM model can be applied to wheat cropping systems to improve N management decisions. The model confirmed that proper timing of N applications can reduce leaching losses, but further tests are required in several wheat growing agro-ecological zones to explore N management options that minimise N leaching losses. Even without measurements and/or modelling of N losses and crop uptake, results of this study for wheat indicate that the 15N stable isotopes can be used on its own to estimate FNUE, but more studies from different soil types and on wheat varieties are required to verify the trends observed in this study.
Dissertation (MSc (Agric))--University of Pretoria, 2017.
Agricultural Economics, Extension and Rural Development
MSc (Agric)
Unrestricted

Waterbirds are often overlooked as predators in aquatic ecosystems, despite the fact that waterbirds congregate in great numbers in and around waterways, notably estuaries. To fully appreciate the effect that aquatic feeding waterbird species may have on aquatic prey communities and the role that they play in estuarine food webs, stable isotopes and fatty acid profiles were employed to examine the seasonal diet of selected waterbirds in the Kowie Estuary, Eastern Cape Province, South Africa. Population counts were conducted every month for four seasons to examine the demography of waterbirds in the lower reaches of the estuary. The mean monthly energy consumption, along with dry matter intake of all waterbird species observed, were calculated and compared to similar estuaries in South Africa and elsewhere. Three duck species, one migrant sandpiper and one piscivore were selected for more detailed investigation at several temporal scales. This thesis has revealed that stable isotope analysis of waterbird tissues provides more informative data than fatty acid analysis for investigating waterbird diet and basal resource-tertiary consumer nutrient coupling. Stable δ15N and δ13C isotopes from several body tissues, in conjunction with SIAR models, were used to determine the seasonal diet of each waterbird species, while fatty acid profiles were investigated to examine the trophic transfer of fatty acids from basal resources to waterbird predators via the benthic fauna. Stable isotopes revealed that Cape Shoveller, Cape Teal and Yellow-Billed Duck shifted their diet over both long and short temporal scales, while the migratory Ruff and piscivorous Little Egret maintained a relatively consistent diet over time. Isopods, amphipods, copepods and Mysidacea were the main foods of all three duck species and the Ruff (>30%). Little Egret fed mainly on flathead mullet throughout the year. Fatty acid analysis revealed evidence for trophic transfer of specific fatty acids from basal resources to waterbirds in the Kowie Estuary but provided little information on seasonal diet of waterbirds. Waterbirds foraging in the Kowie Estuary appeared to shift their diet to coincide with resource abundance pulses, but also displayed seasonal dietary overlap. This study highlights the role that waterbirds play in aquatic food webs. The subject requires more attention so that we can better understand all the predatory drivers on aquatic communities.

L'étude de l'écologie alimentaire des organismes ainsi que l'étude de la structure et du fonctionnement des réseaux trophiques, principale caractéristique de l'organisation des écosystèmes, ne sont pas aisées en environnement marin. Des méthodes indirectes d'étude ont donc été développées récemment, telles que l'utilisation de " traceurs écologiques " qui sont des paramètres (bio)chimiques mesurés dans les tissus biologiques des organismes. Sur la base du postulat " je suis ce que je mange ", les traceurs écologiques constituent des indicateurs relativement fiables du niveau trophique des organismes et/ou de leur zone d'alimentation. Dans un premier temps, l'importance de certains facteurs de variations biologiques et environnementaux des traceurs isotopiques et métalliques (mercure Hg et cadmium Cd) a été étudiée dans le Golfe de Gascogne. Dans un tel environnement marin ouvert, supportant une grande diversité biologique et subissant diverses influences, notre hypothèse de travail était effectivement que les sources de variations sont nombreuses. Cette thèse a ainsi mis en évidence qu'il était nécessaire d'intégrer différents facteurs de variations pour utiliser ces traceurs écologiques dans ce type d'écosystème, tels que le changement de la ligne de base sur un gradient côte-large pour un calcul pertinent des positions trophiques. Dans un second temps, ces outils ont été directement appliqués pour l'étude de l'écologie alimentaire de quelques espèces d'intérêt commercial, telles que la sardine, l'anchois et le bar. Ils ont ainsi révélé une relative spécialisation de la sardine sur certaines proies mésozooplanctoniques, alors que l'anchois montre d'une part une plasticité trophique plus importante sur ce compartiment planctonique, et d'autre part une plus grande flexibilité en termes de zones d'alimentation. Dans le car du bar, dont l'écologie alimentaire était jusqu'à présent très peu connue en dehors des zones côtières, le couplage des données isotopiques (révélant des informations sur le régime alimentaire sur le moyen à long terme) avec des données de contenus stomacaux (révélant des informations sur le court terme) a permis de mettre en évidence la sélectivité des individus de bars adultes sur les petits poissons pélagiques à forte valeur énergétique, lorsque ce prédateur fréquente les eaux du large. Enfin, ces traceurs écologiques ont été utilisés pour affiner la compréhension de la structure et du fonctionnement des réseaux trophiques dans le Golfe de Gascogne, et le comportement de certains contaminants tels que le Hg dans ces réseaux. Plus de 140 espèces provenant des différents réseaux trophiques de cet écosystème ont ainsi été analysées en isotopie, et 120 espèces pour leurs concentrations de Hg dans le muscle. Les traceurs isotopiques en particulier ont révélé que dans cet écosystème : 1) les mammifères marins sont un compartiment structurant des réseaux trophiques ; 2) les chaînes alimentaires sont relativement courtes ; 3) les chaînes alimentaires et les relations trophiques sont fortement organisées en "réseau" ; 4) le degré d'omnivorie est plutôt moyen dans l'écosystème, avec une tendance à l'augmentation chez les niveaux trophiques supérieurs. Ce travail de thèse a également mis en évidence une contamination en Hg plus importante dans le muscle des espèces provenant des habitats profonds du Golfe de Gascogne. Dans un contexte de besoin d'outils de suivi de l'état écologique des écosystèmes marins, et des espèces composant les réseaux trophiques en présence, cette thèse a finalement démontré tout l'intérêt d'utiliser les traceurs écologiques tant à des fins de recherches fondamentales qu'à des fins appliquées en écologie marine.

Face à l’augmentation actuelle des pressions anthropiques sur les réserves d’eaux douces, leur préservation, et notamment celle des eaux souterraines, est primordiale. Les interactions entre les lacs et les eaux souterraines sont étudiées ici afin d’identifier si certains lacs peuvent être utilisés comme indicateurs de changements qualitatifs et quantitatifs des eaux souterraines, spécialement au Québec où plus de 10% du territoire est recouvert d’eaux douces avec un million de lacs recensés. Une vingtaine de petits lacs de Kettle, situés dans des dépôts fluvioglaciaires, ont été spécifiquement choisis pour leur très probable interconnexion avec les aquifères libres peu profonds. Les flux d'eaux souterraines ont été quantifiés via les bilans hydrologiques des lacs couplés aux deux traceurs naturels des eaux souterraines que sont les isotopes stables de la molécule d’eau et le radon 222.A l’échelle régionale, ces lacs présentent un apport annuel et un temps de renouvellement relativement rapide par les eaux souterraines. A l’échelle locale, la modélisation journalière multicouches d’un lac témoin (le lac Lacasse) montre l’importance de la mesure des traceurs, et leur complémentarité, sur la colonne d’eau en fonction des saisons. Différents scénarii d’évolution climatique et environnementale ont ensuite été testés sur les bilans hydrologiques à long terme. Les résultats montrent que la sensibilité de la composition isotopique des lacs à l’horizon 2050 face à l’évolution de la recharge est principalement contrôlée par le pourcentage que représente l’apport des eaux souterraines dans le total de leurs apports en eau, avec une sensibilité optimale pour une fraction de 50 à 80% des apports totaux. Par l’amélioration des connaissances sur les interactions entre lacs et eaux souterraines et sur les outils qui les mettent en évidence, ce travail de recherche a montré que la signature géochimique des lacs peut être utilisée comme indicateur du devenir des ressources en eaux souterraines face aux changements climatiques et environnementaux, pour une meilleure gestion durable de ces hydro systèmes
In the face of modern anthropogenic pressures, the preservation of freshwater resources, particularly groundwater, is paramount. This study investigates interactions between small lakes and groundwater in Quebec, where more than 10% of the territory is covered by freshwater including one million inventoried lakes, to determine whether these lakes may be used as indicators of groundwater change. Twenty-one kettle lakes, set in fluvioglacial deposits, have been specifically targeted for this study due to the high likelihood of connection to shallow unconfined aquifers. Groundwater flows were quantified via lake water balances coupled with two natural tracers of groundwater: stable isotopes of water and Radon-222. On a regional scale the majority of these lakes are characterized by an important annual groundwater inflow and a short-to-medium groundwater flushing time. Daily multi-layer modeling of one of the study lakes, Lake Lacasse, highlights the importance of conducting measurements of these complementary tracers on the water column at the local scale. Different climate and environmental change scenarios were tested to determine the long-term evolution of lake geochemistry. The results indicate that the sensitivity of the isotopic composition of lake water to changes in recharge by year 2050 is mainly controlled by the amount of the total lake balance contributed by groundwater, with an optimum sensitivity for 50-80% of the total inflows contributed by groundwater. This research demonstrates that the geochemical signatures of lakes can be used to indicate future groundwater change in response to climate and environmental evolution, which may assist in improvements to the sustainable management of freshwater resources

Une technique de " spikage ", ou dilution d'isotopes stables multi-élémentaire, a été est développée afin de quantifier et caractériser simultanément les compartiments échangeables de Cd, Zn, Cu, Ni et Pb dans des sols contaminés. Cette technique a étéest ici validée par comparaison avec les résultats de spikage d'isotopes radioactifs de Cd, ainsi que ceux d'extractions chimiques. Par ailleurs, une étude intégrée des signatures isotopiques du Zn (d66Zn) dans plusieurs compartiments d'écosystèmes contaminés (sites métallurgiques de Viviez-Decazeville, S. -O. France et de Kempen, N. -E. Belgique) permet de proposer un schéma cohérent des différents fractionnements isotopiques de Zn liés à son traitement métallurgique. L'existence de différents d66Zn pour le zinc " enrichi " et " résiduel " s'avère donc un outil puissant de localisation de sources de contamination métallurgique. Ces résultats démontrent l'efficacité des isotopes stables comme traceurs en matière de traçage de processus et de source de contamination
A multi-elementary spiking method has been is developpeddeveloped in order to simultaneously quantify and caracterizecharacterize simultaneously the labile pools fraction of Cd, Zn, Ni, Cu and Pb in contaminated soils. This method is has been validated by comparison with 1) radioactive Cd spiking data,g Cd and of2) chemical extractions results. In additionFurthermore, an integrated study of Zn isotopic signatures (d66Zn) in various compartments pools of two contaminated ecosystems (zinc smelting sites of Viviez-Decazeville, S. -W. Of France and of Kempen, N. -E of Belgium) has been performed allowing the identification of various allows to assume a coherent scheme of Zn isotopic fractionations during associated to the metallurgical processes. The differents d66Zn ratio observed in between "enriched" and "residual" zinc would be a powerfull tool to identify the metallurgical contaminations origins. These results demonstrate the efficiency of stable isotopes as tracers for contamination processes and sourcescontaminations tracers

Bibliography: pages 85-96.
Heavy stable strontium isotope ratios (⁸⁷Sr/⁸⁶Sr) may be used to characterize the habitat choices of early hominids. The basis for this approach is that different geological substrata may have a characteristic range of ⁸⁷Sr/⁸⁶Sr ratios in the available soil strontium pool. This range may be represented in the plants growing on these various geologies and thus into the bones of animals feeding in these areas. Through an examination of strontium isotope ratios for isotope and soils from 10 different geologies in the Sterkfontein Valley and immediate vicinity, it was possible to obtain some tentative indication of the possible range in ⁸⁷Sr/⁸⁶Sr ratios in an area most likely to cover favoured foraging habitats of early hominids, such as Australopithecus robustus. On the basis of isotopic data from extensive dolomite sampling, it is clear that there is a wide range of variation in strontium isotope ratios for dolomite substrata around Swartkrans. This may be as a result of topography, water action and atmospheric pollution. However, in spite of such variation, it is possible to distinguish isotopically different habitats, such as riparian from slopes. Such variation will complicate the interpretation of early hominid home ranges, but does provide alternative avenues for behavioural interpretations and also emphasises the necessity for the collection of background isotopic data.

New methods, based on tracer gas measurements and isotopicanalysis can be used to evaluate the moisture properties ofbuilding materials and provide the means for forensic analysisof the origins and history of excessive water in buildings, theimmediate practical consequences of which will be the abilityto improve the moisture performance of constructions. It is shown, in theory and through measurements how thewater vapour permeability of porous building materials can witha good degree of accuracy be estimated with tracer gasmeasurements that provide an efficient alternative to the cupmethod. Complementary measurements may be carried out in orderto evaluate the contribution of surface diffusion and theeventual enhancing effects of moisture content on the diffusioncoefficient. The Random Hopping Model is used to illustrate howthe surface diffusion coefficient depends on the amountadsorbed and the activation energy of migration that can beevaluated from the sorption isotherms. It is explained how the abundance ratios of two of the mostordinary isotopes of hydrogen and oxygen in water can be usedto determine its history. These isotopes are stable and givethe water a distinct signature that can be used to reveal itssource as shown in a case study. In a contrary manner themeasured isotopic separation can be used to determine therelevance of different transport processes and reactions. It isof central importance that not only does the magnitude ofisotopic separation for the reactions vary for deuterium andoxygen-18 but even the ratio thereof. One of the challenges hasbeen to construct an experimental method for retrieving samplesof water for comparison. Furthermore this thesis includes an evaluation of a new typeof a light weight construction with loose-fill cellulose fibre,in which the conventional polyethylene vapour barrier has beenreplaced with polypropylene fabric. With a verified model ithas been investigated how the construction would perform fordifferent internal moisture loads and reference climate fromthe literature. The results suggest that this type ofconstruction is not to be recommended. KEYWORDS:tracer gas, water vapour permeability,diffusion, surface diffusion, isotopic analysis, deuterium,oxygen-18, fractionation, vapour barrier, transient numericalmodelling of diffusion.
QC 20100611

The oxygen isotope ratio of dissolved inorganic phosphate (δ18Op) represents a novel and potentially powerful stable isotope tracer for biogeochemical research. Analysis of δ18Op may offer new insights into the relative importance of different sources of phosphorus within natural ecosystems. Due to the isotope fractionations that occur alongside metabolism of phosphorus-containing compounds, δ18Op could also be used to better understand the intracellular and extracellular reaction mechanisms that control phosphorus cycling. In this thesis, new methods were developed and tested for the extraction of dissolved inorganic phosphate (Pi) from freshwaters and its isolation from other oxygen-containing compounds, including nitrate, sulfate and dissolved organic matter. Excluding contaminant sources of oxygen during δ18Op analysis is a critical analytical challenge that has constrained δ18Op research in freshwaters to date. These new methods were evaluated against existing protocols for analysis of δ18Op. While the protocol developed in this thesis exhibited greater accuracy and precision for freshwater matrices compared to the traditional approach reported by McLaughlin et al. (2004), further development work is required to increase the accuracy of this protocol compared to that reported by Gooddy et al. (2016). Through the application of δ18Op within two exemplar freshwater ecosystems in this thesis, the in-stream fate of Pi derived from the effluent of a wastewater treatment plant and from groundwater discharge was examined. Within both ecosystems, δ18Op revealed the occurrence of metabolic processes that influenced the in-stream fate of P yet were masked in the hydrochemical data. In addition, the data reported here increase the worldwide groundwater δ18Op dataset nearly threefold. These groundwater data highlight the important potential differences in δ18Op due to bedrock geology, alongside the potential to use δ18Op to better understand the importance of groundwater-derived P following discharge to surface water ecosystems.

Les écosystèmes marins côtiers subissent de nombreuses perturbations naturelles et anthropiques. Dans le contexte socio-économique actuel, mieux comprendre le fonctionnement et transfert des contaminants dans ces écosystèmes est primordial. L’étude du transfert de la matière organique et des contaminants aux interfaces, constitue un enjeu crucial. Les principaux objectifs sont de caractériser l’ichtyofaune des herbiers de posidonie et comprendre les relations trophiques ; d’établir les niveaux et variabilité spatiale de la contamination en éléments traces ETs et polluants organiques persistants POPs dans les compartiments de l’écosystème ; et d’identifier les sources et les processus influençant les niveaux de contamination le long du réseau trophique à Marseille et Hyères. La caractérisation du peuplement de poissons et des relations trophiques au sein de l’écosystème est nécessaire pour comprendre les niveaux de contamination. Chez les poissons, le phénomène de bioaccumulation des ETs est difficile à mettre en évidence, excepté pour le mercure. L’influence du régime alimentaire, taille et besoins physiologiques et métaboliques est manifeste. La grande stabilité et la rémanence des POPs leur confèrent des propriétés de bioconcentration et de bioamplification importantes. Les concentrations en contaminants mesurées, ainsi que la détection de pesticides toxiques interdits, attestent de la nécessité de considérer cette pollution avec attention, plus forte à Marseille
The marine ecosystems undergo frequent disturbances. In the current socio-economic context characterized by intensive urban development and industrialization, it is of primordial importance for the management of the environment to achieve a better understanding of the functioning and the transfer of contaminants within these ecosystems. The study of the transfer of organic matter and contaminants to the interfaces is thus a crucial issue. The main objectives are to characterize the fish fauna and to determine the food webs; to establish the levels and patterns of spatial variability of contamination by trace elements TEs and persistent organic pollutants POPs; and to identify the sources and the processes having an influence on the levels of contamination throughout the food webs. The characterization of the fish populations and the trophic relations between the compartments of the ecosystem is necessary in order to understand the levels of contamination in TEs and POPs. For the fishes, it is difficult to provide evidence of the phenomenon of bioaccumulation of TEs, except for mercury, but the influence of diet, size and physiological and metabolic requirements is obvious. The great stability, liposolubility and persistence of the POPs confer on them significant bioconcentration and bioamplification capabilities. The concentrations in TEs and POPs recorded, and the detection of banned toxic pesticides, attest to the necessity of paying close attention to this pollution

Four prograding reef terraces (6, 15, 30, and 50 m) have been repetitively exposed to marine and freshwater alteration during the Pliocene and Pleistocene periods. Prolonged freshwater alterations have resulted in many diagenetic overprints that obscure early diagenetic products. This study investigates the sequence of the diagenetic processes and products in the terrace deposits using five long cores and 14 short cores taken from these different reef terraces. The lithologic changes in the cores were documented for reconstruction of the original depositional frameworks prior to embarking on a diagenetic study. Both textural and geochemical changes were examined within all four different terraces in order to characterized the diagenetic history. The textural changes observed in the cores and thin sections, provided preliminary evidence of the diagenetic environment. Through the use of X-ray diffractometry, stable isotopes (C and O), and trace element data, the interpretation of the diagenetic environment can be constrained. The reef terraces were deposited as as shallowing upward units following a down-stepping carbonate sequence. The lithology of the cores is dominated by reefal facies, which consist of the back reef, reef crest, front, and fore reef facies. The exposure surfaces, observed at various depths, constrained the interpretation of early diagenetic environments (met. vadose and phreatic). Three major diagenetic environments can be characterized from the cores, these are meteoric vadose, meteoric phreatic, and dolomitizaton. These diagenetis environments produced different geochemical signatures, which can be quantified through analysis of the stable isotopes and trace elements incorporated into the cements. The different reef terraces represent different duration of exposure, with the higher terraces having been exposed longer than the lower ones. This study enables the documentation and comparison of the processes and products of the meteoric diagenesis that occurred within these different terraces. In addition, this study also constrain the early dolomitization observed in sigmoidal reef deposits. In order to further quantify the process of early dolomitization, mineralogy, isotopes C and O, trace elements, and the Sr-isotopes were examined as well.

Les récifs coralliens de Nouvelle-Calédonie constituent un « hot-spot » de biodiversité marine et sont classés au patrimoine mondial de l’Unesco depuis 2008. Ces récifs sont dans un bon état général, mais ils sont soumis à des pressions anthropiques de plus en plus intenses, engendrées par un développement industriel (mines de nickel) et urbain croissant.Mieux comprendre le fonctionnement des écosystèmes lagonaires calédoniens est donc devenu un enjeu majeur. Ce travail s’inscrit dans cette démarche, avec pour objectifs principaux : (1) de reconstruire l’architecture des réseaux trophiques de ces écosystèmes (méthode des isotopes stables), (2) de déterminer leurs niveaux de contamination en éléments traces métalliques et en polluants organiques, et (3) de décrire l’intégration et le cheminement de certains de ces contaminants en leur sein. L’étude des écosystèmes récifo-lagonaires et de leurs réseaux trophiques a été réalisée au travers du prisme de prédateurs méconnus de hauts rangs trophiques : les poissons anguilliformes (murènes, congres et poissons-serpents). Pour ce faire, différentes sources de matière organique (MO) et divers consommateurs, parmi lesquels les poissons anguilliformes, ont été prélevés dans plusieurs sites répartis sur un gradient côte-large et provenant de deux zones du lagon sud.Quatre réseaux trophiques ont été identifiés au cours de ce travail. La voie benthique basée sur la MO du turf algal est la voie trophique majeure, commune à tous les poissons anguilliformes. L’utilisation complémentaire de la voie benthique sédimentaire et de la voie « pélagique lagonaire », est également mise en évidence avec une importance variable selon les espèces. En revanche, la MO provenant des phanérogames marines n’est intégrée qu’indirectement, par le biais de la voie détritique. Les différentes espèces d’anguilliformes appartiennent donc à des réseaux trophiques en partie divergents selon leur habitat (substrat dur ou meuble) et leur régime alimentaire (micro-, macrocarnivore ou piscivore). Ces prédateurs de hauts niveaux trophiques, consommant principalement des crustacés et des poissons mais également occasionnellement des annélides polychètes et des céphalopodes, se révèlent pour la plupart opportunistes. Une compétition entre certaines espèces est soulignée par le recouvrement de leurs niches trophiques. Les sources de MO et les consommateurs récifaux du lagon calédonien accumulent des concentrations modérées à fortes en éléments traces d’origine agricole, urbaine et minière. La bioaccumulation dépend des propriétés physico-chimiques du contaminant lui-même et des caractéristiques propres à l’organisme (taille, habitat, régime alimentaire, etc.). Ainsi, les contaminants sont répartis différemment entre les compartiments, et seuls Hg et As sont bioamplifiés le long des réseaux trophiques. Une contamination du lagon par les polluants organiques est également soulignée. Bien que les concentrations mesurées chez les poissons anguilliformes restent relativement faibles, l’étendue spatiale de cette contamination, ainsi que la détection de pesticides très toxiques dont l’utilisation est interdite (DDT), attestent de la nécessité à considérer cette pollution avec attention. Toutes ces considérations renforcent l’importance de mener un suivi à long terme des contaminations d’origines diverses en relation avec le fonctionnement trophique des systèmes récifo-lagonaires
New Caledonian coral reefs constitute a « hot spot » of marine biodiversity and were registered World Heritage by UNESCO in 2008. These reefs are in good health, but they are subject to intense anthropic threats, induced by the increase of industrial (nickel mining) and urban development. A better understanding of the functioning of the Caledonian coral reefs has become a major issue. This work is part of this approach, with as main goals to: (1) reconstruct the architecture of food webs of these ecosystems (stable isotope method), (2) determine their contamination levels in metallic and organic contaminants and (3) describe integration and pathways of some of these contaminants through the food webs. The description of ecosystems and their food webs was carried out by the study of unknown predators: the anguilliform fish (moray, conger and snake eels). Different sources of organic matter (OM) and consumers, including anguilliform fish, were sampled in several sites distributed over a coast to barrier reef gradient within two areas of the south lagoon. Four food webs were identified. The benthic pathway based on the algal turf OM is the main food web, common to all anguilliform fish. The complementary use of benthic sedimentary (SOM) and “lagoon pelagic” (POM) food webs, is also highlighted with variable importance according to species. In addition, OM from seagrasses is included indirectly by the detrital pathway. The numerous anguilliform fish species belong to diverse food webs in part, depending on their habitat (hard and/or soft bottom) and their diet (micro/macro carnivores or piscivores). These predators of high trophic level, consuming mainly crustaceans and fish but also more occasionally annelids and cephalopods, are mostly opportunistic. A competition between some species is underlined by the overlap of their trophic niches. Sources of OM and consumers of the Caledonian coral reefs accumulate moderate to strong concentrations of trace elements issued from agricultural, urban and mining origins. Bioaccumulation depends on both physical and chemical properties of the contaminant and the organism’s own characteristics (size, habitat, diet, etc.). So, contaminants are distributed differently between compartments and only Hg and As are biomagnified along food webs. Contamination of the lagoon by organic pollutants is also pointed out. Even if concentrations measured in anguilliform fish are rather low, widespread contamination, plus the detection of toxic and forbidden pesticides (DDT), confirm the necessity to include this pollution in further studies. All these considerations reinforce the importance of setting up a long-term tracking system of contamination from diverse origins, linked with the trophic functioning of food webs

We test the fidelity of shallow-water gastropod skeletons as multi-proxy archives of seasonal paleo-environmental change by performing isotopic and trace-metal analyses on specimens of Conus ermineus from the Gulf of Mexico. Four adult specimens were collected from Stetson Bank in the Flower Garden Banks National Marine Sanctuary during the summer of 2002. Shell samples were milled along axes of growth to produce time-series profiles spanning up to eight years. We corrected the profiles for growth rate effects and compared the tuned results with in situ temperature and salinity records at the reef surface and temperature profiles from nearby surface buoys. Examination of sample densities in δ18O cycles shows that shell growth is faster during summers and slower during winters. Tuning the profiles versus time yields δ18O values that co-vary closely with seasonal temperatures to a high degree of coherency (R2 = 0.84). The δ13C profiles show cyclic variation modified by ontogenetic decreases in δ13C. These ontogenetic trends are attributable to decreasing metabolic efficiency, while seasonal cycles reflect hydrographic changes in the gastropods’ habitat. Salinity and δ13C of dissolved inorganic carbon show a strong correlation at Stetson Bank (R2 = 0.80), and early summer shell δ13C minima coincide with local salinity minima during times of peak river discharge. The terminations of these δ13C minima occur during annual upcoast reversals of shelf currents in this area. These effects are augmented by summer stratification and productivity minima that further decrease seawater δ13C. Sr/Ca ratios increase through ontogeny, most likely due to decreasing metabolic efficiency. However, seasonal variations in Sr/Ca profiles show strong similarity with δ18O profiles, confirming the temperature dependence of Sr/Ca and minimal influence of salinity on shell δ18O at Stetson Bank. The results of this study show that tuned δ18O and Sr/Ca profiles can be used to reconstruct seasonal paleotemperatures. Carbon isotope profiles and environmental data also demonstrate the utility of Conus δ13C as a proxy for freshwater flux and shelf circulation.