Le soufre existe dans l’hydrosphère dans des état d’oxydation allant des sulfates (+VI) aux sulfures (-II) et incluant de nombreuses espèces à des états d'oxydation intermédiaires, telles que le soufre élémentaire (0), les thiosulfates (-I, V) et les sulfites (IV). Ces espèces en particulier sont considérées comme des intermédiaires importants dans les réactions biologiques et abiotiques qui transforment (oxydent, réduisent ou dismutent) le soufre et sont fréquemment couplées aux cycles biogéochimiques du carbone, de l’azote, de l'oxygène et du fer.Les processus du cycle du soufre sont étudiés en mesurant les concentrations des différentes espèces contenant du soufre (analyse de spéciation) et en mesurant leur rapport isotopique respectif (analyse isotopique). Des difficultés analytiques sont fréquemment rencontrées, car les espèces soufrées, notamment celles de valence intermédiaire, sont présentes en faibles concentrations et sont difficiles à isoler. Ainsi, les rapports isotopiques des espèces de valence intermédiaire sont rarement déterminés. Les études des processus du cycle du soufre gagneraient grandement à l'amélioration des méthodes de mesure des rapports isotopiques des espèces de soufre inorganiques, en particulier des espèces intermédiaires les moins abondantes.Dans ce contexte, ce travail de thèse s’est consacré à l’élaboration de stratégies analytiques combinant spéciation et isotopie du soufre, afin de réaliser la mesure des rapports isotopiques du soufre de plusieurs espèces inorganiques présentes simultanément dans des échantillons liquides. Une méthode de spéciation permettant de quantifier les sulfites, les sulfates et les thiosulfates par chromatographie liquide couplée à un spectromètre de masse à plasma à couplage inductif haute résolution (LC-HR-ICP-MS) a tout d’abord été mise en place. Ensuite, une approche hors-ligne a été développée pour l’analyse isotopique des sulfures, des sulfates et des thiosulfates. Elle consiste en une préparation d’échantillon par précipitation séquentielle des espèces soufrées, suivie de leur analyse par analyseur élémentaire couplé à un spectromètre de masse à rapport isotopique (EA-IRMS). Cette méthode permet de déterminer les valeurs de δ34S des sulfures, des sulfates et des thiosulfates avec des incertitudes de mesure inférieures à 0,5 ‰ pour des échantillons d’eau contenant au moins 27 µg de soufre. Cette méthode a été appliquée à l’étude d’eaux de source et d’eaux d’un aquifère profond et au suivi du fractionnement isotopique du soufre dans une culture de bactéries sulfato-réductrices.Un couplage entre séparation anionique et détection par spectromètre de masse à plasma à couplage inductif multicollecteur (LC-MC-ICP-MS) a été mis au point pour la détermination en ligne des valeurs de δ34S des sulfites, des sulfates et des thiosulfates. Cette méthode nous a permis de déterminer δ34S des sulfites, des sulfates et des thiosulfates pour des échantillons d’eau contenant 1 µg de soufre par espèce avec des incertitudes de mesure inférieures à 0,6 ‰. / Sulfur is present in the hydrosphere at oxidation states ranging from sulfate (+VI) to sulfide (-II) and including many species at intermediate oxidation states, such as elemental sulfur (0), thiosulfate (-I, V) and sulfite (IV). These species in particular are considered as important intermediates in biological and abiotic reactions (oxidation, reduction or disproportionation) involving sulfur and are frequently coupled to the biogeochemical cycles of carbon, nitrogen, oxygen and iron.Sulfur cycle processes are studied by measuring the concentrations of different species containing sulfur (speciation analysis) and by measuring their respective isotope ratios (isotopic analysis). Analytical difficulties are frequently encountered because sulfur species, especially intermediate valence species, are present in low concentrations and are difficult to isolate. Thus, the isotope ratios of intermediate valence species are rarely determined. Methods for measuring isotope ratios of inorganic sulfur species, particularly the least abundant intermediate species, would be a great assistance in deciphering sulfur cycle processes.In this context, this thesis work was devoted to the development of analytical strategies combining speciation and isotopic analysis of sulfur, in order to measure sulfur isotope ratios of several inorganic species that can be simultaneously present in liquid samples. First, a speciation method for quantifying sulfite, sulfate and thiosulfate by liquid chromatography coupled to high-resolution inductively coupled plasma mass spectrometer (LC-HR-ICP-MS) was set up. Then, an off-line approach was developed for the isotopic analysis of sulfide, sulfate and thiosulfate. It consisted of a sample preparation by sequential precipitation of the sulfur species, followed by elemental analyzer coupled to isotope ratio mass spectrometer (EA-IRMS) analysis. This method made it possible to determine the δ34S values of sulfide, sulfate and thiosulfate with measurement uncertainties below 0.5 ‰ for water samples containing at least 27 µg of sulfur. This method has been applied to the study of spring waters and deep aquifer waters and the monitoring of isotopic fractionation of sulfur in a culture of sulfate-reducing bacteria.Moreover, an on-line analytical method coupling anionic separation and detection by multicollector inductively coupled plasma mass spectrometer (LC-MC-ICP-MS) has been developed for the determination of δ34S values of sulfite, sulfate and thiosulfate. This method allowed us to determine δ34S of sulfite, sulfate and thiosulfate for water samples containing as little as 1 µg of sulfur per species with measurement uncertainties below 0.6 ‰.

A escassez de trabalhos acerca dos impactos causados por mosaicos agrícolas sobre a biodiversidade dificulta a criação de estratégias de conservação, havendo necessidade de informações acerca da ecologia e comportamento de espécies da fauna. Nesse contexto o presente estudo objetivou: 1) determinar a composição e estrutura de assembleias de mamíferos de médio e grande em uma paisagem agrícola de Mata Atlântica; 2) avaliar o padrão de alimentação da onça-parda (Puma concolor) por meio da análise de isótopos estáveis (SIA) em dois mosaicos agrícolas; 3) analisar por meio da diversidade funcional (FD) assembleias de mamíferos em remanescentes florestais distribuídos nas principais regiões biogeográficas da Mata Atlântica, e identificar limiares ecológicos para a conservação. Para o inventário, foram selecionados oito remanescentes florestais na Região Metropolitana de Campinas (RMC), São Paulo. Os dados foram coletados por busca ativa (visualizações e vestígios), resultando no registro de 34 espécies de mamíferos, sendo 27 de médio e grande porte, quatro de pequeno porte, e três exóticas. Sete espécies se encontram ameaçadas de extinção, com registros inéditos de Myrmecophaga tridactyla e Lycalopex gymnocercus. A riqueza e a composição de espécies registradas apontaram a RMC como importante para a conservação da mastofauna. Foram analisados isotopicamente (carbono e nitrogênio) pelos de onças-pardas, obtidos a partir de amostras fecais coletadas por busca ativa em remanescentes florestais inseridos em paisagens agrícolas no interior do estado de São Paulo. Houve maior consumo de presas C3 (~47% dos indivíduos) na área com maior proporção de vegetação nativa, e maior consumo de presas C4 (~40% dos indivíduos) para a área onde é predominante a matriz agrícola. Foi constatado o consumo de presas com dieta baseada em itens alimentares dos remanescentes e da matriz agrícola, sugerindo alta plasticidade comportamental das onças-pardas e de suas presas ocupando áreas fortemente impactadas pelo homem. A ferramenta isotópica apresentou informações pioneiras sobre ecologia trófica, podendo contribuir na elaboração estratégias de conservação em áreas antropizadas. Para a análise da FD e identificação dos limiares foi utilizado um banco de dados composto por 49 assembleias de mamíferos, criado a partir de dados primários e secundários de inventários, sendo selecionadas 38 características das espécies para o cálculo. A existência de limiares foi verificada utilizando a função \"segmented\", disponível no programa R. A FD apresentou-se diferente para assembleias com o mesma riqueza de espécies, indicando que filtros ambientais podem influenciar nos valores. O incremento gradual na FD devido ao aumento da área dos remanescentes mostrou uma relação positiva, possivelmente ligada a maior complexidade e heterogeneidade de áreas maiores. Foram identificados dois limiares (52 e 1244 ha), criando três situações funcionalmente distintas, tanto críticas quanto mais estáveis, permitindo definir e propor formas de ação específicas. Assembleias presentes entre os limiares apresentaram incremento funcional significativo entre FD e o aumento da área dos remanescentes, e ações visando à restauração e melhorias na configuração da paisagem devem ser incentivadas. Conclui-se, portanto, que tanto a SIA quanto a FD, podem ser consideradas importantes ferramentas para delinear estratégias e ações em prol da conservação da mastofauna. / The scarcity of studies regarding the impacts of agricultural mosaics on biodiversity hinders the creation of conservation strategies and a need for information concerning the ecology and behavior of wildlife species. In this context, the present study aimed to: 1) determine the composition and structure of mammal assemblages of medium and large sized in an agricultural landscape at Atlantic Forest; 2) evaluate the puma (Puma concolor) feeding pattern through analysis of stable isotopes (SIA) in two agricultural mosaics; 3) analyze mammal assemblages by functional diversity (FD) in forest remnants distributed in major biogeographic regions of the Atlantic Forest, and identify ecological thresholds for conservation. For mammal\'s inventory, eight forest remnants were selected in Campinas Metropolitan Region (RMC), São Paulo state. Data were collected through active search (visualizations and tracks), resulting in the record of 34 mammal species, 27 medium and large size, four of small size, and three exotic. Seven species are threatened with extinction, with novel records of Myrmecophaga tridactyla and Lycalopex gymnocercus for this region. The species richness and composition pointed RMC as an important area for mammal\'s conservation. Carbon and nitrogen stable isotopes were analyzed in pumas hair, obtained from fecal samples collected by active search in forest remnants embedded in agricultural landscapes in São Paulo state. There was a higher consumption of C3 prey (~ 47% of individuals) in the area with the highest proportion of forest coverage, and greater consumption of C4 prey (~ 40% of individuals) where the agricultural matrix was predominant. Was observed the consumption of prey with diet based on food items from both forest remnants and agricultural matrix, suggesting high behavioral plasticity of puma\'s and their prey\'s occupying areas heavily impacted by man. Stable isotopes contributed with pioneer information on trophic ecology, aiming the development of new conservation strategies in anthropogenic areas. A database consisting of 49 mammal\'s assemblages, created from primary and secondary data of inventories, was used for FD analysis and threshold\'s identification. 38 specie\'s traits were selected for FD calculation. The thresholds existence was verified using the \"segmented\" function, available on R program. FD was different between mammal assemblages with the same species richness, indicating that environmental filters may affect its values. The gradual increment in FD, due to the increase in forest remnants area, presented a positive relationship, possibly linked to the increased complexity and heterogeneity of large areas. Two thresholds (52 and 1244 ha) were identified, creating three functionally distinct situations, both critical as more stable, allowing to define and propose for each one specific ways of action. Mammal\'s assemblages found between the thresholds showed significant functional increment considering the relationship between FD and forest remnants area, and actions aiming biological restoration and improvements in the landscape configuration should be encouraged. It was concluded, therefore, that both SIA as the FD can be considered important tools to outline strategies and actions for mammal\'s conservation.

The spread of surface coal mining has resulted in loss of forests in the Appalachian region. The Forestry Reclamation Approach (FRA) was developed to provide guidance for restoring forests on reclaimed mined land. This study hypothesizes that the FRA will result in larger magnitude of sediment accumulation rates in reclaimed mine sites compared to those reclaimed using grassland reclamation. Three sediment cores and six trenches were sampled within four reclaimed mined and three previously logged sites in eastern Kentucky. Samples were processed for radionuclides, grain-size, stable isotopes (δ13C), and POC. LIDAR data were used to identify valley fills, while historical aerial photography was used to identify changes in vegetative cover from 1994 to 2016. Radionuclide dating was used to determine sediment accumulation rates over the previous 100 years. Results from logged sites are inconclusive. δ13C data for all sites fall within the range expected for forested landscapes (C3), and do not show any transitions from grassland to forests. POC data indicates that inventories and fluxes were the same for mined and logged sites. Sediment accumulation rates for reclaimed mined lands show elevated values after the implementation of the FRA, compared to grassland reclamation, thus supporting the hypothesis for previously mined sites.

The Avar were nomadic people from Central Asia who migrated into the Carpathian Basin in Central-Eastern Europe during the mid to late Migration Period (AD 568 - 895). Archaeological evaluation of grave goods and documentation of mortuary practices have been the primary means of understanding the Avar. However, this approach has largely neglected skeletal and biochemical analysis, in particular as these approaches relate to the biological variation, ancestry, and dietary patterns of the Avar. There remains debate as to whether disparities existed among the socially stratified Avar population of ancient Hungary. It is argued by some that these disparities existed and were the result of differential access to nutritional resources. This hypothesis was tested using the unique properties of isotopes and their chemical signatures. In so doing, the qualitative work on the grave goods was augmented by an additional, quantifiable line of evidence. To investigate social stratification among the Avar population, the techniques of chemical multi-isotope and osteological analysis were employed. Multi-isotopic analyses can be done on stable isotopes (carbon, nitrogen, and oxygen) and on the heavy isotopes (strontium and lead). The particular stable isotopes examined were carbon (δ13C), nitrogen (δ15 N), and oxygen (δ18O). The heavy isotopes analyzed were strontium (87Sr/86Sr) and lead (206Pb/204Pb). Stable isotope analysis as well as ratio analysis of the heavy isotopes strontium (87Sr/86Sr) and lead (206Pb/204Pb) are well-established analytical chemistry methods for examining diverse aspects of diet and mobility through specific geographic regions. The analysis was performed on samples derived from well-preserved tooth enamel and bones. Reconstructing migration and dietary patterns at the Sajópetri cemetery site has helped estimate variability among social groups and between sexes in this population at the time of the Migration Period. Results of the heavy isotope analysis revealed that the Avar population were non-locals to the region, and the stable isotope analysis demonstrated that there was little variation between social groups with slightly higher variation between sexes. This research provides an empirical and analytical framework for further research into migration patterns and social class dynamics of late prehistoric Hungry. This study also adds existing research possibilities to the on-going biogeochemical studies conducted throughout Europe.

This thesis deals with a medieval material from Rounala in Karesuando parish, Norrbotten county, Lapland. The aim is to reconstruct the diet and mobility patterns. It is through carbon, nitrogen and sulphur stable isotopes and radiocarbon that both pastoralist traits and whether which part Christianity played in the burial traditions of these human remains is being studied. Another aim is to discuss the repatriation issue as these remains are subjected to. The results mainly show that all individuals had a mixed diet and no pastoral way of living has been established. Furthermore, individual 3 is suffering from pathological changes. With radiocarbon dates ranging from 1300 to 1720 AD, two groups can be distinguished as to whom had been buried before and after the construction of the church. And repatriation is being discussed as an issue to who have ownership over ancient remains.

Metal played important role in the social and economic development of societies since its discovery. It is so important that the some part of humankind historical development were designated by the type of metal which was extensively used depending upon the level of technology of that period enabling the processing of metal like bronze age and iron age. In this frame, the rich metal deposits of Anatolia made this region a very important metal working and civilization center. K&uuml / ltepe where it was the center of the trade organization in Anatolia realized between Assur and Anatolia during 1945-1730 B.C called Assyrian Trade Colonies Period was one of the most important metal working center of Anatolia at that period. In this thesis, it is aimed to make a contribution to understand the metal working technology in K&uuml / ltepe by examining the uncovered metal artifacts dated to that period. For this purpose, the metal artifacts uncovered from K&uuml / ltepe Ancient Site belonging to Colonies Period which are exhibited in the Anatolian Civilization Museum were examined by portable XRF (PXRF) to obtain the quantity of elements that constituted the artifacts without giving any harm to the artifact. Besides the examination of exhibited artifacts in the Anatolian Civilization Museum, the uncovered metal artifact parts belonging to Colonies Period which are not suitable for exhibition and separated for studying were examined by energy dispersive X-ray unit of scanning electron microscope for elemental analysis and by X-ray diffraction for the analysis of minerals. The microstructures of artifacts were examined by scanning electron microscope and optical microscope for revealing the operations on metal applied by ancient metalsmith. In addition to analysis mentioned above, in order to make a contribution to understand the copper trade between K&uuml / ltepe and its environs lead isotope analysis of some samples from the separated metal artifacts for studying was also performed. As a result of all those analyses, it was concluded that K&uuml / ltepe ancient metalsmiths in Colonies Period had the knowledge to smelt the copper and to pour molten metal into a mold to produce an object of desired shape. Moreover, they also discovered that the addition of some elements to copper hardens the structure. In this frame the bronze to be obtained by deliberately adding of tin to copper was attained. In addition, they were aware of shaping the casted object by hammering. In the meantime, they had the knowledge of heat treatment that allows them forging the object many times till giving the desired shape without causing the fracture in the structure.

Moose populations in southern Manitoba have declined. Although the primary cause of this decline is unclear, wolf predation is considered a main contributor because wolves have limited moose populations elsewhere. To help understand the role of wolf predation in limiting moose populations we reconstructed the proportional diet of wolves using stable isotope analysis and a Bayesian stable isotope mixing model (MixSIAR). We tested the assumptions of MixSIAR by running sensitivity analyses on trophic discrimination and prior information. We observed differences in wolf diet in areas where moose and deer coexist and are spatially separated, with changes both seasonally and annually. Our results suggest white-tailed deer were preyed on during winter, even in areas where deer are locally rare, suggesting prey catchability is more important than local prey density. Seasonal changes in prey accessibility strongly affect wolf predation rates, and manipulating alternative prey populations could mitigate predation impacts on moose. / October 2015

The past few years have seen an upsurge in the use of renewable biomass as a source of energy due to growing concerns over greenhouse gas emissions caused by the combustion of fossil fuels and the need for energy independence due to depleting fossil fuel resources. Although coal will continue to be a major source of energy for many years, there is still great interest in replacing part of the coal used in energy generation with renewable biomass. Combustion converts inherent chemical energy of carbonaceous feedstock to only thermal energy. On the other hand, partial oxidation processes like gasification convert chemical energy into thermal energy as well as synthesis gas which can be easily stored or transported using existing infrastructure for downstream chemical conversion to higher value specialty chemicals as well as production of heat, hydrogen, and power. Devolatilization or pyrolysis plays an important role during gasification and is considered to be the starting point for all heterogeneous gasification reactions. Pyrolysis kinetic modeling is, therefore, an important step in analyzing interactions between blended feedstocks. The thermal evolution profiles of different coal-biomass blends were investigated at various heating rates using thermogravimetric analysis. Using MATLAB, complex models for devolatilization of the blends were solved for obtaining and predicting the global kinetic parameters. Parallel first order reactions model, distributed activation energy model and matrix inversion algorithm were utilized and compared for this purpose. Using these global kinetic parameters, devolatilization rates of unknown fuel blends gasified at unknown heating rates can be accurately predicted using the matrix inversion method. A unique laboratory scale auto-thermal moving bed gasifier was also designed and constructed for studying the thermochemical conversion of coal-biomass blends. The effect of varying operating parameters was analyzed for optimizing syngas production. In addition, stable carbon isotope analysis using Gas Chromatography-Combustion-Isotope Ratio Mass Spectrometry (GC-C-IRMS) was used for qualitatively and quantitatively measuring individual contributions of coal and biomass feedstocks for generation of carbonaceous gases during gasification. The predictive models utilized and experimental data obtained via these methods can provide valuable information for analyzing synergistic interactions between feedstocks and also for process modeling and optimization.

Coral reefs are highly complex and also highly threatened ecosystems. Population growth and the unsustainable use of coral reefs have resulted in 55% of the world’s reefs being considered degraded. Fishing, the primary ‘local’ threat on most reefs, has altered the composition of most reef communities. As a result, very few pristine coral reefs remain. Typically, coral reef research is done via underwater visual censuses, providing abundance estimates but no indication of trophic interactions, therefore we know relatively little about the structure of intact reef food webs. Understanding how human activities affect trophic structure and feeding interactions among resident reef species may be important for coral reef conservation. Here, I apply stable isotope analysis to coral reef piscivorous fishes from Kiritimati (Republic of Kiribati), the world’s largest atoll. I examine dietary niche metrics of five focal species (Cephalopholis argus, Cephalopholis urodeta, Aphareus furca, Lutjanus bohar, and Lutjanus fulvus) and of the piscivore functional group as a whole, across an anthropogenic disturbance gradient that results from the atoll’s heavily skewed geographic population distribution. Using bootstrapped stable carbon (δ13C) and nitrogen (δ15N) isotope values, controlled for body size effects and analysed with Bayesian methods using the SIAR (Stable Isotope Analysis in R) program, I provide evidence of isotopic niche differentiation in C. argus and L. fulvus relative to other sampled species in terms of niche width metrics and mean δ13C and δ15N values. I also analyse the effect of fishing pressure at an individual level (controlling for body size effects on stable isotope signatures for each species), population level (accounting for observed differences in body size distributions across the fishing pressure gradient for each species), and the ‘community’ level (accounting for body size and relative abundance differences of the five piscivores across the fishing pressure gradient). These metrics reveal species-specific changes in niche metrics of three of the focal species at the individual level: C. urodeta, showed regionally distinct niche width metrics but no apparent correlation with fishing pressure, while A. furca and L. bohar, both had broader niche width metrics in heavily fished areas. No significant effect of fishing pressure was found at population or community levels. This study provides the first evidence using stable isotopes that fishing can alter the diets of coral reef fishes. The mechanism by which it can do so, while not entirely clear, would most likely be by expanding a given species’ dietary diversity by either forcing it to switch to non-preferred prey items or changing the diet and/or body size of its prey items, both of which would reflect significant ecological changes within a community. This thesis provides evidence of the utility of stable isotope analyses in answering important ecological questions in coral reef food webs, and reveals that fishing can affect reef communities at the most fundamental level of trophic interactions. / Graduate / 0329 / burrilladrian@gmail.com

High Arctic permafrosted soils represent a massive sink in the global carbon cycle, accounting for twice as much carbon as what is currently stored as carbon dioxide in the atmosphere. However, with current warming trends this sink is in danger of thawing and potentially releasing large amounts of carbon as both carbon dioxide and methane into the atmosphere. It is difficult to make predictions about the future of this sink without knowing how it has reacted to past temperature and climate changes. This dissertation summarizes the results of the first study to look at long term, fine scale organic carbon delivery by the high-Arctic Colville River into Simpson’s Lagoon in the near-shore Beaufort Sea. Modern delivery of organic carbon to the Lagoon was determined to come from a variety of sources through the use of a three end-member mixing model and sediment biomarker concentrations. These sources include the Colville River in the western area of the Lagoon near the river mouth, marine sources in areas of the Lagoon without protective barrier islands, and coastal erosional sources and the Mackenzie River in the eastern area of the Lagoon. Downcore organic carbon delivery was measured on two cores in the Lagoon, one taken near the mouth of the Colville River (spans about 1800 years of history) and one taken on the eastern end of the Lagoon (spans about 600 years of history). Bulk organic parameters and biomarkers were measured in both cores and analyzed with Principle Component Analysis to determine long-term trends in organic carbon delivery. It was shown that at various times in the past, highly degraded organic carbon inputs of what is likely soil and peat carbon were delivered to the Lagoon. At other times, inputs of fresher, non-degraded, terrestrially-derived organic carbon inputs of what are likely higher amounts of plant and vegetative material was delivered to the Lagoon. Inputs of degraded soil carbon were also shown to correspond to higher temperatures on the North Slope of Alaska, likely indicating that warmer temperatures lead to a thawing of permafrost and in turn organic carbon mobilization to the coastal Beaufort Sea.