Human and faunal osteological material from the southeastern Carpathian Bend area, Romania, was analysed for δ13C, δ15N and δ34S to reconstruct the dietary practices of the Middle Bronze Age Monteoru culture. As a secondary objective, the extent of intraskeletal variation in stable isotope values was investigated by comparing skeletal elements with differing collagen turnover rates. The intraskeletal isotope results revealed a pattern where cortical bone samples produced statistically lower δ13C values compared to trabecular bone samples, highlighting the necessity for more systematic research to understand how stable isotopes are incorporated into bone collagen of various skeletal elements. Diet in the Monteoru culture was shown to be exclusively or predominantly terrestrial in origin with no detectable input of C4 or marine resources. Differences in average δ13C and δ15N values between the two sites included in the study (representing distinct phases of the culture) suggest a shift in dietary preferences from a more meat-based economy to a more dairy- and plant-based economy. The dissimilar contribution of animal foods to overall diet between the two sites was supported by estimates generated by the Bayesian mixing model FRUITS, which also showed that in both sites plant foods accounted for most of the calories consumed. The faunal isotopic data contained a few outliers, suggestive of deliberate movement of livestock, either through long-distance herding or trade. A combined approach using juvenile bone collagen and incrementally sectioned tooth dentine from adults demonstrates that the duration of breastfeeding varied between individuals, but that there were no significant differences in weaning practices between survivors and non-survivors. Sulphur isotopes reflect a population that was relatively homogeneous in its isotopic composition and local in origin, except for the presence of two possible migrants. The δ13C and δ15N data from the Carpathian Bend are comparable to those from contemporaneous sites in coastal and inland Greece and Croatia, suggesting a broad uniformity in Bronze Age dietary practices across Southeast Europe. As the first major stable isotope study conducted on osteological material from the Romanian Sub- Carpathians, this thesis provides new insights into the lives of these communities, expands our knowledge of Bronze Age subsistence strategies in Southeast Europe, and establishes a foundation for further isotopic investigations in the region.

Dentre os herbicidas atualmente comercializados, o glifosato é um dos mais utilizados no Brasil. A eficácia do glifosato, bem como de outros herbicidas, no combate às ervas daninhas, esbarra nos problemas que esses compostos acabam proporcionando ao meio ambiente. Embora estudos venham sendo realizados para elucidar melhor o comportamento de herbicidas no meio ambiente, a complexidade do comportamento desses compostos abre caminho para realização de um número significativo de trabalhos de pesquisa. Nesses estudos, é rotineiro o uso de compostos radiomarcados (traçadores radioativos) para avaliar a biodisponibilidade no solo. Todavia, o emprego, manipulação e estocagem de compostos radiomarcados exigem cuidados sob o ponto de vista da segurança, razão pelo qual o uso de isótopos não radioativos é uma tendência internacional, especialmente em pesquisas de campo. Dentre desse contexto, o trabalho descreve um método para a síntese do glifosato enriquecido no isótopo estável do nitrogênio (15N). A sintese do herbicida-15N foi realizada utilizando-se da reação de fosfometilação com diaquil fosfito e glicina-15N. Os testes foram realizados em microescala e em quantidades equimolares. Nas condições estabelecidas, foi possível alcançar um rendimento de reação de aproximadamente 25%. A otimização das condições de sintese, empregando a técnica isotópica, deverá disponibilizar uma importante ferramenta a ser utilizado em estudos referentes ao comportamento do glifosato no sistema solo-planta / Among the actual commercialized herbicides, the glyphosate is one of the most used in Brazil. Its efficiency, as well as the others herbicides, on weeds control is attached to problems that this composts cause to the environment. Although studies about the herbicides behavior in the environment have been done, the complexity of this composts behavior leads to the accomplishment of an expressive number of research works. In these works, it?s common the use of radio labeled compounds (radioactive tracers) to evaluate its bio-availability in the soil. However, the use of this radio labeled composts, its manipulation and storage demands a careful handling in the chemical security point of views. This is the reason the use of non radiactive isotopes is an international tendency, especially for field researches. According to this context, the present work describes a method for the synthesis of enriched glyphosate for the nitrogen stable isotope (15N). The tests were undertaken in micro-scale and in equimolar quantities. Under these established conditions, the reaction reached the yield of approximately 25%. The optimization of the synthesis conditions with the use of isotopic techniques shall offter an important tool to be used in studies that are referred to glyphosate behavior in soil- plant system

Orientador: Antenor Zanardo / Banca: Jorge Silva Bettencourt / Banca: Roberto Peres Xavier / Banca: Sebastião Gomes de Carvalho / Banca: Maria Margarita Torres Moreno / Resumo: A Mina Granusso está situada nas proximidades de Cordeirópolis/SP e constitui uma fonte importante de matéria-prima para o Pólo Cerâmico de Santa Getrudes. No local aflora uma sucessão de rochas da Formação Corumbataí (Permiano Superior) constituída na base por lamitos maciços que gradam para ritmitos siltosos, passando para um horizonte psamo-pelítico e culminando em uma seqüência de ritmitos siltoarenosos. Uma feição particular é a presença de zonas de alteração hidrotermal, associadas a veios quartzo-carbonáticos e fraturas, que impuseram às rochas alterações químicas, mineralógicas e texturais. Estudos petrográficos, químicos e de DRX indicam que após a compactação mecânica houve injeção de fluidos diagenéticos em um sistema de fraturas originando veios de quartzo de baixa cristalinidade e enriquecimento de sílica de horizontes silto-arenosos. Uma nova injeção fluidal impulsionada pela ação do magmatismo basáltico acelerou a formação de albitas e deu origem a veios com calcita, quartzo, clorita e pirita. Os dados de d18O e d13C mostram que os carbonatos se precipitaram de um fluido isotopicamente homogêneo sem variações drásticas de temperatura. Valores de d13C entre -8,1 a -4,5 (PDB) indicam uma fonte profunda para o CO2 que deu origem a calcita enquanto que valores de d18O entre +18,9 e +24,1 (SMOW) sugere interações sucessivas do fluido com a rocha hospedeira e abaixamento de temperatura. / Abstract: The Granusso mine is located near the Corderopolis city and constitutes an important source of raw material to the Santa Gertrudes Ceramic Cluster. Late Permian sedimentary rocks of the Corumbataí Formation outcrops in the area. The litological succession comprises a sequence of massif, banded to laminate siltstone topped by carbonate to sandy siltstone. Hydrothermal alteration is an important feature generally associated with host rock whitening. A large basaltic sill intruded the sequence and affected the evolution of the diagenetic and hydrothermal process. Petrographic, chemical and XRD dates suggest that after the mechanical compaction a fluid injection caused the precipitation of low-cristalinity quartz and silica enrichment of sandy-siltstone horizons. A new fluid injection driven by the Serra Geral magmatism triggered albite formation and gave rise to the pyrite-chlorite-quartzcalcite veins. Carbon and oxygen isotope studies of the host rocks and veins show that carbonate precipitated from a homogeneous fluid without strong changes in temperatures along hydrothermal conducts. d13C values of -4,5 to -8,1 (PDB) indicate a CO2 deep-source while d18O of +18,4 to +24,1 (SMOW) and the positive correlarion beetween d18O and d13C values suggest a temperature-dependent trend accompanied by a progressively increasing of fluid/rock interaction. / Doutor

Dentre os herbicidas atualmente comercializados, o glifosato é um dos mais utilizados no Brasil. A eficácia do glifosato, bem como de outros herbicidas, no combate às ervas daninhas, esbarra nos problemas que esses compostos acabam proporcionando ao meio ambiente. Embora estudos venham sendo realizados para elucidar melhor o comportamento de herbicidas no meio ambiente, a complexidade do comportamento desses compostos abre caminho para realização de um número significativo de trabalhos de pesquisa. Nesses estudos, é rotineiro o uso de compostos radiomarcados (traçadores radioativos) para avaliar a biodisponibilidade no solo. Todavia, o emprego, manipulação e estocagem de compostos radiomarcados exigem cuidados sob o ponto de vista da segurança, razão pelo qual o uso de isótopos não radioativos é uma tendência internacional, especialmente em pesquisas de campo. Dentre desse contexto, o trabalho descreve um método para a síntese do glifosato enriquecido no isótopo estável do nitrogênio (15N). A sintese do herbicida-15N foi realizada utilizando-se da reação de fosfometilação com diaquil fosfito e glicina-15N. Os testes foram realizados em microescala e em quantidades equimolares. Nas condições estabelecidas, foi possível alcançar um rendimento de reação de aproximadamente 25%. A otimização das condições de sintese, empregando a técnica isotópica, deverá disponibilizar uma importante ferramenta a ser utilizado em estudos referentes ao comportamento do glifosato no sistema solo-planta / Among the actual commercialized herbicides, the glyphosate is one of the most used in Brazil. Its efficiency, as well as the others herbicides, on weeds control is attached to problems that this composts cause to the environment. Although studies about the herbicides behavior in the environment have been done, the complexity of this composts behavior leads to the accomplishment of an expressive number of research works. In these works, it?s common the use of radio labeled compounds (radioactive tracers) to evaluate its bio-availability in the soil. However, the use of this radio labeled composts, its manipulation and storage demands a careful handling in the chemical security point of views. This is the reason the use of non radiactive isotopes is an international tendency, especially for field researches. According to this context, the present work describes a method for the synthesis of enriched glyphosate for the nitrogen stable isotope (15N). The tests were undertaken in micro-scale and in equimolar quantities. Under these established conditions, the reaction reached the yield of approximately 25%. The optimization of the synthesis conditions with the use of isotopic techniques shall offter an important tool to be used in studies that are referred to glyphosate behavior in soil- plant system

The boreal chorus frog (Pseudacris maculata) is a widespread species but we know little of its ecology. I examined the nature and existence of competitive mechanisms operating between larvae of the boreal chorus frog and wood frog (Lithobates sylvaticus) from field, mesocosm and laboratory venues spanning nutrient concentrations. I assessed larval performance and diet of tadpoles at natural ponds by measuring tadpole growth and size at metamorphosis, and stable isotope ratios for carbon and nitrogen in tadpole tissue to examine if patterns were consistent with the operation of interspecific competition. In mesocosms I measured chorus frog performance in relation to wood frog presence and nutrient enrichment to confirm the occurrence of competition and examine whether nutrient conditions typical of agriculture ponds impact tadpole performance. In the field I compared larval performance and relative abundance between agricultural ponds and those in Elk Island National Park, to examine whether habitat features surrounding ponds in farmlands reduces the abundance of tadpoles and whether tadpole performance results in reduced abundances. Lastly, I examined whether chemical interference by wood frogs occurs by raising chorus frog tadpoles with caged wood frog tadpoles and/or their feces in the laboratory. Chorus frog performance was reduced by presence and abundance of wood frog tadpoles. Resource partitioning in natural ponds and overlap in mesocosms, based on stable isotopic analysis, suggest that resource competition occurs. In mesocosms chorus frog performance was reduced by wood frog tadpoles in fertilized treatments and nutrient conditions at agricultural sites are not in themselves detrimental to these anurans. Performance of chorus frog tadpoles in agricultural ponds was unaffected, whereas wood frogs were larger at metamorphosis in crop ponds. Reduced tadpole abundances of both species at these ponds may be related to habitat features or conditions in croplands. The existence of chemical interference in the absence of physical interaction was confirmed, as chorus frogs exposed to wood frog tadpoles and/or feces had reduced growth and were smaller at metamorphosis which could reduce terrestrial survival and future reproduction. My research contributes to our knowledge on boreal chorus frog ecology and our general understanding of competition between larval anurans. / Ecology

This thesis addresses the utility of deep-water coral geochemistry and its potential to reconstruct oceanographic conditions in the Straits of Florida. Through stable isotope and elemental analyses of the carbonate skeletons and use of available geochemical proxy calibration equations, present and past environmental parameters were determined. Over the last several years, scientific expeditions to the bottom of the Straits of Florida have revealed hundreds of deep-water coral mounds and led to the collection of extensive oceanographic data, sediment samples, and deep-water coral specimens. In 2005-2006, an Autonomous Underwater Vehicle (AUV) was used to map the coral mound fields at five sites with the use of geophysical imaging technology, and the manned Johnson-Sea-Link II submersible was deployed for further exploration and sample collection. The AUV and the submersible CTD also measured numerous environmental parameters, including temperature and salinity. With the goal of reconstructing environmental parameters across the Straits of Florida, Scleractinian and gorgonian deep-water coral specimens were selected from three sites spanning the Straits. Each coral was sampled at the highest resolution possible and analyzed for stable isotopes and elemental concentrations. Resulting geochemical data, specifically d18O, d13C, Sr/Ca, and Mg/Ca, was then used with previously published and newly developed calibration equations to calculate temperature, salinity, and seawater density. Kinetic and vital effects were also examined and taken into account while reconstructing environmental parameters using the coral geochemistry. Additional reconstructions using stable isotopic values from benthic foraminifera corroborated the geochemical reconstructions, and analyses of pteropods and surface sediment samples provided further insight into the oceanographic conditions at the bottom of the Straits of Florida. Results from geochemical reconstructions agreed with in situ data, indicating that slightly warmer bottom temperatures exist on the eastern side of the Straits and salinity variability among the three sites is minimal. This suggests that the deep-water coral skeletons are sensitive recorders of the environmental conditions in which they lived. Ultimately, in situ measurements and reconstructed parameters showed that there is little variability across the bottom of the Straits and that Antarctic Intermediate Water (AAIW) is the only apparent water mass in the area at that depth. Moreover, comparison of the coral habitat from this study with others from around the world demonstrated that certain conditions are required for deep-water coral growth, and that these same parameters are common to deep-water reef systems throughout the globe. Further sampling and geochemical analyses of deep-water corals in the region may be used to gain additional insight into the oceanographic conditions surrounding the coral mounds both presently and in the past. As with other previously studied deep-water coral systems, this highlights the potential for the reconstruction of paleo environmental records from deep-water corals in the Straits of Florida.

Many large terrestrial ecosystems have patterned landscapes as a result of a positive feedback system between vegetation communities and environmental factors. One example is tree island habitats in the Florida Everglades. Although they only occupy a small portion of the Everglades landscape, tree islands are important features as the focus of nutrient accumulation and wildlife biodiversity in the Everglades ecosystem. The hardwood hammock community on the elevated head of tree island habitats can accumulate high phosphorus concentration in the otherwise P-limited Everglades ecosystem. In this dissertation, I examined two hypotheses derived from the chemohydrodynamic nutrient accumulation model, which suggests that high transpiration of tree island hammock plants is the driving force for nutrient accumulation in tree island soil. According to this model, I hypothesized that tree islands with lower dry season transpiration should have less phosphorus accumulated than the tree islands with higher dry season transpiration. By examining the water use and nutrient status from 18 tree islands in both slough (perennially wet) and prairie (seasonally wet) locations, I was able to compare water availability and nutrient accumulation in slough and prairie tree islands with different marsh hydroperiods. Chapter 1 uses elemental and stable isotope analysis to look at water stress and nutrient concentration in tree island plants. I showed that the prairie tree island plants suffer from drought stress during the dry season, when the marshes in the prairies dry out. Prairie tree islands also have lower soil and plant P concentration than the slough tree islands. Moreover, I showed that foliar N isotope ratio serves as a stable proxy for community level P availability for tree island plants, and prairie tree island plants have less P available than slough tree island plants. In Chapter 2, I showed that the satellite imagery derived normalized difference water index (NDWI) provides a robust indicator of community level canopy water content of these tree islands. NDWI, used as a proxy for water status, was positively related to foliar N isotope ratio, which suggests that water availability is linked to nutrient availability in the tree island hardwood hammock plant communities. These findings are consistent to the chemohydrodynamic nutrient accumulation model. In Chapter 3, I used sap flow sensors on individual trees to provide a real-time measurement of plant transpiration. I showed that tree island plant transpiration is affected by multiple factors including weather fluctuations, marsh water depth regulated by local water management, and canopy structure of different tree islands. Overall, my dissertation establishes a link between tree island plant water use and nutrient accumulation. It could be potentially important for future restoration plan of tree islands and Everglades hydrological management.

In 1987, Burney and collaborators (Journal of Archaeological Science (1994) 21, 273–281) recovered a ca. 8 m sediment core from the western basin of Laguna Tortuguero, Puerto Rico that spanned the last ca. 7000 calibrated years. They produced a detailed microscopic charcoal record, and from an initial peak in charcoal at ca. 5300 cal yr B.P. suggested that humans had colonized the island some 2000 years earlier than documented by the archaeological evidence then available. In 2008, two sediment cores were recovered from the eastern basin of Laguna Tortuguero. AMS dates on macrofossils indicate the profile extends to 7600 calibrated years, but it includes an interval with missing sediment marked by a layer of shell hash and bracketed by radiocarbon dates of 5144 and 1648 cal yr B.P. Stable carbon and nitrogen isotopic analyses show evidence for a drastic change in depositional environment following this event. Microscopic charcoal concentrations peak just below and at the contact of the shell hash, with the first of three high-charcoal levels positioned immediately above the date of 5144 cal yr B.P. The microscopic charcoal record appears to support the interpretations of Burney et al. (1994) of human colonization around 5300 cal yr B.P., although the fires recorded in the Laguna Tortuguero sediments may also be driven by regional climate shifts. Desiccation of Laguna Tortuguero, a hurricane or multiple hurricanes, or a tsunami could explain the missing sediments and the large change in depositional environment that occurs above the shell hash. AMS dating of sediment from the mud-water interface at the 2008 core site suggests a possible hard-water effect of ca. 1200 cal yr for dates on the algal gyttja above the shell hash, which if true would mean that the event that deposited the shell hash may have occurred as late as ca. 448 cal yr B.P. (A.D. 1502).

Tree-ring analyses have contributed significantly to investigations of climate change and climate cycles, including the North Atlantic Oscillation (NAO), Pacific Decadal Oscillation (PDO) and El Niño/Southern Oscillation (ENSO). Stable isotope climate proxies (?18O, ?D, and ?13C) have enhanced traditional ring-width data, although poor preservation of ancient wood has generally constrained reconstruction of stable isotope proxy records to the Holocene and Late Pleistocene. An opportunity to apply these stable isotope methods to older wood has been presented by recovery of remains of Mixed-Coniferous Boreal Vegetation, in Early Pliocene (4-5 Ma) deposits at Strathcona Fiord, Ellesmere Island, Canada (~79°N). An exceptionally well-preserved tree trunk, identified as Larix (larch) through wood anatomical characteristics, from this high Arctic site provided a 203-year tree-ring record, from which we present the first high-resolution, secular isotope record of Pliocene climate. ?18O, ?D, and ?13C isotope values indicate a variable climate with alternating intervals of cool/wet to warm/dry weather. These fluctuations in climate may be attributable to phase changes in climate cycles observed in the record. A growing season mean temperature of 14.4 °C was calculated from isotopic analysis of gastropod shells. Palaeoclimatic modeling of tree isotope values has revealed growing season temperatures of 11-15 °C, and estimated isotope values of precipitation of 18.3 (?18O) and 228 (?D). Both palaeotemperature estimates and source water calculations are comparable to those found in a modern Boreal Forest. Time-series wavelet analysis was applied to these data revealing prominent short (<10 years), intermediate (16-35 years) and long-term (~45-50 years) cyclicity. These are the highest resolution climate cycles recovered from the pre-Holocene terrestrial record, providing evidence for decadal scale cyclicity similar to the NAO and/or PDO 4-5 million years ago.

Identifying the ecological mechanisms that determine food web structure is critical for understanding the causes and consequences of diversity. The objective of this thesis was to identify the mechanisms structuring aquatic food webs across environmental gradients from a multi-level perspective (individual to ecosystem) using integrative methodology and field experiments to test classic ecological theory. My results demonstrate support for the dynamic constraints hypothesis, which predicts habitats with greater disturbance should have shorter food chains, but are not consistent with the ecosystem size hypothesis that predicts larger ecosystems have longer food chains. Insect and amphibian richness increased with increasing pond size and hydroperiod, indicating that insertion of new consumers into pond communities was driving variation in food-chain length. A multivariate analysis testing the influence of physicochemical variables on food-web characteristics revealed that hydroperiod and pond area had a strong influence on amphibian and invertebrate assemblages, trophic diversity and 15N range. Food-chain length did not respond strongly to any one variable, but instead responded weakly to multiple environmental variables, suggesting interacting influences on food-web structure. Conversely, the trophic niche of amphibian larvae was not influenced by pond hydroperiod, but did exhibit ontogenetic diet shifts. Populations of amphibian larvae with broader niche widths also had increased individual variation, supporting the niche variation hypothesis. In addition, I assessed whether species diversity influenced the magnitude of cross-habitat resource flow between aquatic and terrestrial habitats via emerging aquatic insects, metamorphosing amphibians, and litter deposition. Deposition into ponds far exceeded carbon exported via insect and amphibian emergences. We found a negative relationship between resource flux and the diversity of amphibians and insects, which contradicts the general pattern of positive biodiversity-ecosystem function relationships. My research strongly suggests environmental variation is a key process in shaping food-web structure and function and that multiple methodologies are needed to understand temporal and spatial dynamics of aquatic ecosystems.