Human activity modifies the behaviour of large vertebrates and their acquisition of key resources. Despite the predation risk and competition for similar food resources that humans impose, wildlife consumers must acquire key foods across the landscape. Predation risk can modify foraging behaviour, yet we know little about the potential consequences, especially on large spatial scales. Humans may also affect food availability for wildlife by competing for shared prey, which most current harvest prescriptions fail to recognize. Against this background of threats to consumer-resource interactions, my research employed new conceptual, analytical, and practical approaches to seek not only new generalizable insight but also applied solutions. Addressing these goals, I characterized foraging behaviour by grizzly bears (Ursus arctos horribilis) on a focal prey, Pacific salmon (Oncorhynchus spp.), at multiple spatial scales. I predicted how human activity – both as modifications to landscapes and as salmon harvest – might affect bear-salmon interactions. I co-conceived, designed, and carried out this work through a framework of community engagement, which I crafted in collaboration with Indigenous communities in coastal British Columbia (BC). The framework (Chapter 2) identifies how scientists and communities can engage throughout the research process to work towards shared priorities, despite potential challenges in differences of knowledge systems or capacities. Methodologically, I used ratios of stable carbon (δ13C) and nitrogen (δ15N) isotopes in bear hair to estimate relative contributions of salmon in the annual diet of bears and employed existing data on landscape modification and salmon fisheries (i.e., escapement and catch) to characterize human activity and to measure associated variation in salmon consumption by bears. My first empirical contribution (Chapter 3) characterized spatial patterns of annual salmon consumption by grizzly bears across BC. I found substantial differences in salmon consumption within and among grizzly and black (U. americanus) bears in a large coastal region and across BC. Visualizing variation in consumer-resource interactions could guide conservation and management efforts that seek to protect predator-prey associations and marine subsidies for terrestrial ecosystems. I also investigated potential drivers of salmon consumption by bears in interior and coastal watersheds that varied in disturbance (Chapter 4). I found that human footprint in riparian areas of salmon-bearing watersheds affected bear diets more than the amount of salmon biomass available, showing that human activity can disrupt an otherwise strong predator-prey association. My community-based research occurred at the scale of a single large watershed, where I demonstrated how the Wuikinuxv First Nation might design their salmon management prescriptions according to their cultural values (Chapter 5). Despite a reduced abundance of salmon in the area, I identified harvest options that would trade-off benefits to local people and bears equally. In general, my dissertation research contributes to our understanding of the role humans increasingly play in mediating consumer-resource interactions. I also highlight how scientific research can support the leadership that local management can provide in mitigating human impacts to sustain an iconic predator-prey interaction of ecological, economic, and cultural importance. / Graduate / 2020-04-23

Many predatory species cause negative impacts on human interests by threatening game, livestock or human safety. These impacts can create conflicts where stakeholders differ over wildlife management and when one party is perceived to exert their interests at the expense of the other. Finding effective methods to mitigate conservation conflicts requires an interdisciplinary perspective that investigates (i) the reality of the apparent impacts, (ii) the efficacy of any methods intended to remedy them and (iii) the perceptions, motivations and objectives of key stakeholders. In this thesis, I investigated a conservation conflict in the U.K. surrounding predators and game management. I did so with specific reference to the common buzzard Buteo buteo, a species that, due to predation of released pheasants Phasianus colchicus, is both subject to illegal persecution and on- going controversy concerning the licenced selective removal of ‘problem individuals’. I first review the literature to assess the ecological evidence that certain ‘problem individuals’ can be both disproportionately responsible in impacts upon human interests and more likely to reoffend. I show that while there is evidence for these animals across many different taxa, the benefits of their removal can sometimes be short-lived. I highlight possible indirect impacts of selective management and identify it as a potential compromise between different stakeholder groups. Next, I evaluate the performance of Bayesian stable isotope mixing models (BSIMMs) in quantifying the diets of wild animals. By comparing indirect and direct observations of buzzard foraging, I demonstrate that, with the correct selection of trophic discrimination factors, stable isotope analyses can provide a reliable picture of dietary composition that mirrors direct observations. I then apply these mixing models to evaluate the ecological basis of selective removal of ‘problem buzzards’. The results suggest that the consumption by buzzards of released pheasants is not limited to release pens where gamekeepers perceive buzzard predation to be a problem. However, I then show that stable isotope analysis of blood sampled from two of the four buzzards caught inside pens indicates frequent consumption of released pheasants, relative to the rest of the buzzard population. These results suggest that, while some pheasant consumption may go undetected, selecting only buzzards inside pens for removal is likely to target ‘problem birds’. I then investigate buzzard foraging and breeding ecology on land managed for pheasant shooting. I find that buzzards nest at higher density in areas with greater abundances of pheasants and rabbits Oryctolagus cuniculus. However, records of provisioning from nest cameras showed that only rabbits were caught in proportion to their abundance and only rabbit provisioning rate was associated with buzzard productivity. I suggest that the positive relationship between buzzard and pheasant abundance, although seemingly unconnected to pheasant predation, might influence how gamekeepers perceive buzzard impact. Next, I conduct semi-structured interviews on the subject of predator control with 20 gamekeepers across the south of England, to explore the underlying beliefs, norms and information sources that motivate their behaviour. From these interviews, I identify a number of separate, but interconnected, motivations that influence predator control including professional norms, potential penalties, and interpretations of what is ‘natural’. The influences of these motivations are discussed in detail and a conceptual model, incorporating the theory of planned behaviour, is developed. Finally, the key contributions of this thesis are drawn together and discussed in their wider context. Taken together, the results of this thesis illustrate how predator management occurs simultaneously within social and ecological contexts that incorporate the individual attributes of both predators and people. The results of this thesis have direct implications for the management of predators, the representation of stakeholder perspectives and the design of conflict mitigation measures.

The patterns of human diet and migration of the population of Boğazköy in north-central Anatolia were investigated through the application of carbon (δ13C), nitrogen (δ15N) and sulphur (δ34S) stable isotope analysis of bone collagen. The materials used for this research include human and faunal bone samples dating from the Bronze Age to the Roman period. This is the first isotopic study conducted at Boğazköy and for these time periods in north-central Anatolia. The aim of the research was both to reconstruct the dietary habits and mobility patterns of this community as well as investigating the usefulness of δ34S analysis as a dietary tool in this region of Anatolia. Examining the diet and economy at Boğazköy through an isotopic perspective provides a clearer understanding of the life of the inhabitants of the city and sheds light of the political and sociological changes observed during this period in Anatolia. Analysis across different periods revealed that the Bronze Age stands out with the most enriched δ15N (9.9±0.8‰) and δ34S (12.6±3.0‰) values, suggesting a higher consumption of protein in relation to later periods and/or foreign origin for these individuals. With the exception of the Bronze Age, dietary behaviours were very similar across all phases of occupation and do not differ significantly from those observed at other Anatolian sites. The δ13C (‒18.6±0.4‰) and δ15N (9.0±0.9‰) average values for the Iron Age, Hellenistic and Roman periods suggested a diet predominantly based on C3 terrestrial sources. Variations between individuals, implying the consumption of different levels of animal protein, were not directly connected to sex or age. The δ13C results for several of the domestic animals suggest inclusion of C4 plants in their diets. Slight elevated δ13C values for humans indicates the consumption of these animals or the variability of C3 plant values, which may relate to the aridity of this region. The δ15N results suggest the consumption of low quantities of meat, dairy products and/or the contribution of pulses. The application of δ34S has also provided insight into Boğazköy’s economy by suggesting the use of transhumance as a herding strategy during the Iron Age. The presence of foreigners during the Hittite period is also implied by the δ34S results from the human samples. These indicate a coastal provenance where sea-spray effect was visible; however, the lack of a δ34S baseline data for large regions of Anatolia hinders further interpretation of the results.

The energy density formalism (EDF) is used to investigate two problems. The EDF is a phenomenological method that incorporates as much knowledge of infinite nuclear matter as possible. In this formalism the energy of the nucleus is expressed as a functional of its density. The nucleus energy is obtained by minimizing the function, with respect to the density. In this report, the EDF is used to investigate the mercury isotope shift anomaly following the aforementioned suggestion. Specifically, nucleon densities with different degrees of central depression are generated. Energies corresponding to these densities are obtained. The density with the minimum energy is the preferred one. Based on the findings of the present work, it can be concluded that a central depression in the lighter mercury isotopes does not-appear- to be a possible explanation for the isotope shift anomaly. And the anomaly remains unresolved.

L'altération des lithologies himalayennes a potentiellement impacté le cycle global du carbone. Pour pouvoir contraindre et comprendre les processus qui se sont produits dans l'Himalaya et qui ont affecté ces cycles, nous devons être distinguer les signatures de l'altération du silicate et du carbonate dans la charge dissoute des fleuves de l'Himalaya. Des études antérieures ont tenté de le faire en utilisant diverses méthodes mais il n’existe toujours pas de consensus clair sur l’ampleur et le flux de l’altération du silicate dans l’Himalaya. Cette thèse propose l'utilisation du 40Ca comme traceur pouvant améliorer la quantification du flux d'altération du silicate et du carbonate dans la charge dissoute des rivières himalayennes. Des travaux antérieurs ont montré que le budget de l'eau de mer 40Ca est dominé par une source de manteau, de sorte que les carbonates marins ont une signature homogène de 40Ca indiscernable par rapport à la valeur du manteau. En revanche, la croûte supérieure de silicate devrait avoir développé une composition radiogénique. La différence entre la signature en Ca radiogénique des lithologies de carbonate et de silicate peut donc être utilisée pour différencier l’altération du carbonate et du silicate dans la charge dissoute des rivières. Nous présentons ici une étude géochimique comprenant des analyses de Ca radiogénique des rivières drainant les principales unités lithologiques de l'Himalaya, ainsi que des résultats provenant de sédiments, de substrat rocheux, de sol et de gravier. Nos résultats montrent que les carbonates de l’Himalaya ne présentent pas d’excès de 40Ca radiogénique malgré des signatures très variables 87Sr/86Sr, alors que les sédiments sont radiogènes (+0.9 à +4). Ceci suggère que pour Ca, contrairement à Sr, l'échange isotopique entre les lithologies silicate et carbonate a été minime. La composition en Ca radiogène de l'eau des rivières va de +0.1 dans les captages à prédominance carbonatée à +11 dans les rivières drainant des bassins versants silicatés. Pour les grandes rivières, les estimations du budget relatives à l’altération du silicate et du carbonate sur la base des éléments principaux et la composition en Ca radiogénique tendent à concorder. Cependant, pour certaines rivières plus petites, en particulier celles drainant des bassins à dominance silicatée dans les formations cristallines de HHC et du LH, certaines divergences sont observées. Celles-ci ne peuvent pas être attribuées à une définition imprécise de la composition chimique ou radiogénique en Ca des pôles de mélange utilisés pour la modélisation budgétaire, car les valeurs requises pour résoudre le modèle ne sont pas raisonnables. Ils ne peuvent pas non plus être expliqués par la précipitation de carbonates secondaires dans les rivières car la composition non radiogénique de carbonates suggère que ce processus n'est que mineur. Au contraire, ces différences peuvent être dues à la dissolution des traces de calcite radiogénique contenues dans les lithologies de silicate HHC et LH. Le vieillissement de ce matériau, qui ne représente qu'une infime partie de la surface du captage du silicate, pourrait produire une proportion substantielle du Ca radiogénique et pourrait ainsi avoir une influence significative sur le calcul des budgets de ces bassins à partir des données isotopiques. Néanmoins, comme cet effet est observé principalement dans les bassins à faible taux d’érosion des silicates, son influence sur les estimations du flux global de vieillissement du silicate sera mineure. Plus généralement, les résultats de cette thèse impliquent que le système 40Ca permet une résolution de problématiques qui ne peuvent pas être approfondies avec succès à l'aide d'isotopes Sr dans l'Himalaya. Des travaux supplémentaires sont nécessaires pour définir la gamme complète des compositions de Ca radiogénique dans l’Himalaya afin de répondre clairement aux questions concernant les flux d’altération des silicates / Weathering of Himalayan lithologies has had a potential impact on the global carbon cycle. To be able to constrain and understand the processes that occurred in the Himalayas that affected these cycles, we must be able to distinguish the signatures of silicate and carbonate weathering in the dissolved load of Himalayan rivers. Previous studies have attempted to do this using a variety of methods but there is still not a clear consensus on the magnitude and flux of silicate weathering in the Himalaya. This thesis proposes the use of 40Ca as a tracer that could improve the quantification of the silicate and carbonate weathering flux in the dissolved load of Himalayan rivers. Previous work has shown that the 40Ca budget of seawater is dominated by a mantle source, such that marine carbonates have a homogeneous 40Ca signature indistinguishable from the mantle value. In contrast, the upper silicate crust is expected to have developed a radiogenic composition. The difference between the radiogenic Ca signature of carbonate and silicate lithologies can be therefore used to differentiate between carbonate and silicate weathering in the dissolved load of rivers. Here, we present a geochemical survey, including radiogenic Ca analyses, of rivers draining the main lithological units of the Himalaya, as well as results from sediments, bedrock, soil and gravel. Our results show that Himalayan carbonates exhibit no radiogenic 40Ca excesses despite highly variable 87Sr/86Sr signatures, whereas sediments are variably radiogenic (+0.9 to +4). This suggests that for Ca, unlike for Sr, isotopic exchange between the silicate and carbonate lithologies has been minimal. The radiogenic Ca composition of river water ranges from +0.1 in carbonate dominated catchments to +11 in rivers draining silicate catchments. For large rivers, silicate and carbonate weathering budget estimates based on major elements and radiogenic Ca compositions tend to agree. However, for some smaller rivers, especially those draining silicate dominated basins in the HHC and LH formations, some discrepancies are observed. These cannot be attributed to poor definition of the chemical or radiogenic Ca composition of the endmembers used for budget modeling, as the values required to bring the estimates into agreement are unreasonable. They also cannot be explained by precipitation of secondary carbonates in the rivers as the non-radiogenic composition of the carbonate fraction of sediments suggests that this process is only minor. Rather, these discrepancies may be due to the dissolution/weathering of trace amounts of radiogenic calcite contained within HHC and LH silicate lithologies. The weathering of such material, which represents only a tiny fraction of the area of the silicate catchment, could yield a substantial proportion of the radiogenic Ca and may thus have a significant influence on the isotopically based weathering budgets of these basins. Nevertheless, as this effect is observed primarily in basins with low silicate erosion rates, its influence on estimates of the overall silicate weathering flux will be minor. More generally, the results of this thesis imply that the 40K–40Ca system can resolve issues that cannot be successfully addressed using Sr isotopes in the Himalaya. Further work is needed to define the full range of radiogenic Ca compositions in the Himalaya in order to clearly answer questions regarding silicate weathering fluxes

Os modelos para a formação de plútons alcalinos da Província Alcalina do Sudeste Brasileiro ou Alinhamento Poços de Caldas-Cabo Frio associam a gênese destas rochas a grandes reativações ou a passagem de uma pluma mantélica, registrada pelo traço de um hot spot. O objetivo desta tese é, apresentar novos dados e interpretações para contribuir com a melhor elucidação e discussão destes modelos. Os estudos incluem mapeamento, petrografia, litogeoquímica, geoquímica isotópica de Sr, Nd e Pb e datação 40Ar/39Ar. As intrusões selecionadas correspondem ao Morro Redondo, Mendanha e Morro de São João, no Rio de Janeiro, localizados em posições distintas no alinhamento Poços de Caldas-Cabo Frio. A intrusão alcalina do Morro Redondo é composta majoritariamente de nefelina sienitos e sienitos com nefelina, com rara ocorrência de rochas máficas e é caracterizada por uma suíte alcalina sódica insaturada em sílica, de caráter metaluminosa a peralcalina. Esta intrusão foi datada em aproximadamente 74 Ma (idade-platô 40Ar/39Ar). A intrusão alcalina do Mendanha é composta por diversos tipos de rochas sieníticas, além de brechas e estruturas subvulcânicas, como rochas piroclásticas e diques e caracteriza-se por ser uma suíte alcalina sódica saturada em sílica, de caráter metaluminosa, diferente do que ocorre no Marapicu, este subsaturado em sílica. Esta intrusão apresentou duas idades-platô 40Ar/39Ar distintas de magmatismo: 64 Ma para as rochas do Mendanha e 54 Ma em dique de lamprófiro, registrando magmatismo policíclico. O Morro do Marapicu foi datado em aproximadamente 80 Ma. Já a intrusão alcalina do Morro de São João possui uma ampla variedade de litotipos saturados a subsaturados em sílica, tais como sienitos, álcali-sienitos e monzossienitos (alguns portadores de pseudoleucita), com variedades melanocráticas, tais como malignitos e fergustios. Estas rochas definem suas distintas suítes alcalinas subsaturadas em sílica: Uma de composição sódica e outra potássica. Há também uma suíte alcalina saturada em sílica, definida por gabros alcalinos e shonkinitos. A petrogênese destas intrusões corresponde ao modelo de cristalização fracionada, com assimilação de rochas encaixantes (AFC) como indicado pela alta variabilidade de razões isotópicas de estrôncio. No Morro de São João é sugerido o modelo de mistura magmática. Estas intrusões foram geradas a partir de magmas mantélicos enriquecidos, possivelmente associados à antiga zona de subducção relacionada ao orógeno Ribeira. Em razão das novas idades obtidas, o modelo de hot spot proposto fica prejudicado, visto que o Marapicu é de idade mais antiga das intrusões analisadas, o que era esperado para o Morro Redondo. Alguns modelos projetam plumas mantélicas com aproximadamente 1000 km de diâmetro, o que poderia explicar o Mendanha ser contemporâneo ao Morro de São João. As assinaturas isotópicas obtidas para as intrusões não se associam à assinatura isotópica de Trindade e, caso o modelo de plumas mantélicas seja o correto, a pluma que teria maior semelhança de assinatura isotópica é a pluma de Tristão da Cunha. / The models for formation of alkaline plutons of the Southeastern Brazil Alkaline Province or Poços de Caldas-Cabo Frio Magmatic Lineament, which genetic modeling associates crust reactivations or mantle plumes, with definition of a hot spot track. The objective of this work is to report new data and interpretations to contribute to a better understanding and discussion about the model of alkaline rock generation. The studies involved geological mapping, petrography, litogeochemistry, Sr-Nd-Pb isotopes and 40Ar/39Ar geochronology. The selected alkaline complexes are the Morro Redondo, Mendanha and Morro de São João, located at Rio de Janeiro State. These intrusions are well-distributed along the Poços de Caldas-Cabo Frio Magmatic Lineament. The Morro Redondo alkaline intrusion is composed mainly by nepheline syenites and nepheline-bearing syenites and mafic rocks are rare. It was defined as a sodic silica-undersaturated alkaline suite, with metaluminous to peralkaline characteristics. The intrusion was dated at 74 Ma (40Ar/39Ar plateau age). The Mendanha alkaline intrusion is compose by various types of syenitic rocks, breccias and subvulcanic structures, as pyroclastic rocks and dikes. It was defined by a sodic silica-saturated alkaline suite with metaluminous characterisics. The intrusion presented two distinct 40Ar/39Ar ages for the magmatism: 64 Ma for Mendanha rocks and 54 Ma to lamprophyre dike, which illustrates a polycyclic magmatism. The Morro do Marapicu 40Ar/39Ar age yielded 80 Ma. The Morro de São João alkaline intrusion has a large variety of silica-undersaturated to silica-saturated rocks, as syenites, alkali-syenites and monzosyenites (some pseudoleucite-bearing), with melanocratic varieties, as malignites and ferguites. These rocks defined distinct alkaline silica-undersaturated suggenting sodic and potassic types. There was found an alkaline silica-saturated suite, defined by alkaline gabbros and shonkinites. The petrogenesis of these intrusions corresponds to the fractional crystallization, with assimilation of host rocks, and the crustal contamination is indicated by high variability of Sr isotope ratios. For Morro de São João origin is suggested a K-Na bimodal magma. These intrusions were generated from enriched mantle-derived magmas, possible associated to ancient subduction zone of Ribeira orogen. In terms of the new 40Ar/39Ar data, the hot spot model is not plausible, because the Morro do Marapicu is older than the other studied intrusions. Some models projected mantle plumes with 1000 Km size, what may explain the reason for Mendanha and Morro de São João have the nearly the same age. The obtained isotopic signatures for these intrusions were not associated to Trindade signature and, if the mantle plumes model is correct, the plume that has the most similar signature is Tristão da Cunha.

La recherche a porté sur les contraintes reliées à la modélisation des écoulements des eaux souterraines en aquifère côtier. Dans ces aquifères, la présence concomitante d’eaux douces et d’eaux salées modifient les patrons d’écoulement classiquement représentés par l’équation de Darcy. L’influence de la salinité de l’eau sur ses propriétés (densité) et sur la perméabilité du milieu complexifie la représentation mathématique des équations d’écoulement et la résolution des systèmes d’équations. Par ailleurs, l’influence des hétérogénéités du milieu rend plus difficile et hasardeux le paramétrage des modèles et leur calibration. Pour ce faire, nous avons proposé d’utiliser les résultats d’investigations géophysiques et isotopiques des eaux. Une meilleure description du milieu souterrain et l’imagerie de l’interface eau douce/eau salée peut en effet aider à un meilleur paramétrage et à une validation accrue de la simulation des écoulements des nappes côtières. Les mesures géochimiques telles celles des isotopes du radium ont aidé à la validation des flux et concentrations simulés. Notre approche a été appliquée sur la partie aval de la nappe de la Crau. La comparaison des résultats simulés par le modèle aux données de terrain résultant des suivis réalisés ont montré l’intérêt et l’applicabilité et la validation de notre approche méthodologique / The research has focused on the constraints related to the modeling of groundwater in coastal aquifer. In these aquifers, the concomitant presence of freshwater and saltwater alters the flow patterns typically represented by the Darcy equation. The influence of salinity on density and permeability complex the mathematical resolution of flow equations. Moreover, the influence of heterogeneities of aquifer makes it more difficult and risky the model parameterization and its calibration. We propose to use fort that the results of both geophysical and isotopic investigations. Thus, we hypothesize that the description of the subsurface and the imaging of the freshwater/saltwater can help to setup and validate the simulation of groundwater in coastal aquifers. Also we have shown that geochemical measurements such as radon may help to validate the simulated flow. Our approach was applied on the downstream part of the Crau aquifer. The comparison of simulated results to data resulting from monitoring has shown the usefulness and applicability of our approach.

A cultura do cafeeiro é muito importante para a economia agrícola brasileira e em anos recentes tem avançado para o cerrado do oeste da Bahia. Esta região apresenta condições de solo e clima diferentes daquelas onde a cafeicultura já está estabelecida e, portanto, necessita de reavaliações no seu manejo, principalmente quanto à adubação nitrogenada, visto que vem sendo aplicadas doses muito maiores do que aquelas usuais em outras zonas cafeicultoras. A fertirrigação é muito usada nessa região, permitindo a divisão da dose de nitrogênio (N) em várias parcelas, o que comumente diminui as perdas para o ambiente, principalmente via lixiviação. Entretanto, a redução nas perdas pode não estar ocorrendo devido às altas doses de N aplicadas, à negligência quanto ao momento de maior necessidade de N pelas plantas e às altas taxas de irrigação, o que é indesejável tanto do ponto de vista ambiental quanto do financeiro. A eficiência na absorção do N pelos cafeeiros varia no tempo dependendo das necessidades nos diferentes estádios fisiológicos, o que torna o estudo da evolução de sua absorção essencial para identificar a fase na qual as plantas mais necessitam deste nutriente. Através deste conhecimento é possível planejar melhor o parcelamento das aplicações, melhorando a eficiência do uso deste nutriente. Do mesmo modo, é importante encontrar a dose de N que seja simultaneamente mais eficiente em termos de quantidade de N absorvido do fertilizante pelos cafeeiros e de produção de grãos de café. Dentro desta perspectiva um experimento foi desenvolvido para estudar a eficiência da fertilização do N e avaliar momento e dose mais adequados para sua aplicação, no município de Barreiras, Bahia na safra 2008/2009. Os tratamentos escolhidos foram: 0, 200, 400, 600 e 800 kg ha-1 de N, em delineamento inteiramente casualisado com quatro repetições. Foi usada ureia enriquecida em 1,035 átomos % de 15N via fertirrigação a cada 14 dias, dividindo-se cada dose em 26 partes iguais. A concentração de N e abundância de 15N foram avaliadas ao longo do tempo nos diferentes compartimentos do sistema solo-planta para descobrir o momento de maior necessidade deste elemento pela planta. Também foi realizado o balanço de N ao final do ano agrícola para se encontrar o destino do N aplicado como ureia. Estes estudos mostraram que é possível diminuir as doses comumente utilizadas em cafeeiros adultos no oeste baiano de 600 a 800 kg ha-1 de N para 400 kg ha-1 de N sem perda de produtividade. Esta menor dose deve privilegiar o estádio anterior ao de enchimento de grãos, que é o de maior consumo de N por folhas e frutos. A dose de 800 kg ha-1 de N apresentou absorção de luxo e a maior perda de N por lixiviação. / The coffee crop is very important for the Brazilian agribusiness and in recent years the coffee cultivation has been shifted to other non traditional growing areas as the cerrado plains of the Bahia state, which presents different soil-climate conditions in relation to other traditional coffee growing areas. The management procedures have to be re-evaluated, mainly those of nitrogen (N) application since high rates have up to now been used without any scientific support. Fertigation is very much used in this region and allows a high number of splitting, decreasing losses to the environment. However, the use of rates much higher than those applied in traditional growing areas and the high irrigation rates can be leading to expressive leaching losses, which are malefic from both economic and environmental points of view. The N absorption efficiency of the coffee plant varies in time depending on the physiological stage of the crop, so that the study of the evolution of the N absorption becomes essential to identify the moment at which the plant needs more nutrient and so better plan the partitioning of the application to avoid possible losses. In the same way it is important to find out the rates that are simultaneously more efficient in terms of the quantity of absorbed fertilizer N in relation to productivity. Within this perspective an experiment was carried out to study the efficiency of the nitrogen fertilization and evaluate the most adequate time and dose for its application, in Barreiras, BA, Brazil. Chosen treatments were: without N application, 200, 400, 600 and 800 kg ha-1 of N, distributed in a randomized design with four replicates. Urea solutions enriched to 1.035 atom % 15N were applied via fertigation in 14 day intervals, splitting the above mentioned doses in 26 equal parts. The N concentration and 15N abundance data were evaluated along time for the different compartments of soil-plant system to discover the moment of major N need by plant, and a complete N balance was made at harvest time. These studies showed that it is possible to decrease the commonly used fertilization rate of 600-800 kg ha-1 of N applied to adults coffee plants, to 400 kg ha-1 of N. This lower rate should be privileged up to fruit filling, that was found to be the moment of greatest N consumption by leaves and fruits. The rate of 800 kg ha-1 year-1 N presented luxury absorption and presented a major quantity of N lost by leaching.

Conselho Nacional de Desenvolvimento CientÃfico e TecnolÃgico / Os traÃadores naturais oxigÃnio-18 e deutÃrio foram utilizados para identificar caracterÃsticas dinÃmicas das reservas hÃdricas subterrÃneas na Bacia Sedimentar do Araripe, atravÃs da anÃlise de amostras de Ãgua coletadas em 40 poÃos nos meses de janeiro, abril, julho e outubro de 2011. Os pontos de amostragem localizam-se em 08 municÃpios e medidas de condutividade elÃtrica, que expressa salinidade das Ãguas, tambÃm foram realizadas. Os resultados mostram variaÃÃo espacial e temporal dos parÃmetros analisados, mas a mÃdia dos valores de δ18O em amostras de 33 poÃos à de -3,22  0,05 (â) que à o valor mÃdio das chuvas atuais na regiÃo. As amostras dos sete poÃos restantes apresentaram maiores flutuaÃÃes e quatro deles apresentaram valores abaixo de -3,2â. As retas meteÃricas, que expressam medidas de deutÃrio versus oxigÃnio-18, construÃdas com valores de cada coleta mostram coeficiente angular com mÃdia de 7,87  0,60 â cerca do valor da Reta MeteÃrica Mundial. O excesso de deutÃrio cresceu no perÃodo de amostragem de 7,26 a 9,38 â refletindo processos internos no aquÃfero. As amostras com valores de δ18O em abaixo do das Ãguas meteÃricas atuais mostram mistura de paleoÃguas jà identificadas com Ãguas de recargas modernas; as amostras com estes valores nÃo sÃo distinguÃveis pelas suas condutividades elÃtricas que estÃo na faixa das amostras atuai caracterizando a importÃncia dos traÃadores isotÃpicos. / The natural tracers deuterium and oxygen-18 were used to identify the dynamic characteristics of the groundwater reserves in the Araripe Sedimentary Basin, through the analysis of water samples collected in 40 wells in January, April, July and October 2011. The sampling points are located in 08 municipalities and electrical conductivity measurements, which expresses water salinity, were also performed. The results show spatial and temporal variation of the parameters analyzed, but the average values of δ18O in samples from 33 wells is -3.22  0.05 (â) which is the average rainfall in the region today. Samples of the remaining seven wells showed higher fluctuations and four had values below -3.2 â. The meteoric lines that express measures of deuterium versus oxygen-18, constructed with values of each sample show a mean slope of 7.87  0.60 â about the value of the World Meteoric Line. The excess of deuterium in the sample period increased from 7.26 to 9.38 â reflecting internal processes in the aquifer. Samples with values of δ18O in meteoric waters below the current mix of show paleowater already identified with modern recharge water, the samples with these values are not distinguishable by their electrical conductivities that are current in the range of samples characterizing the importance of isotopic tracers.

No presente trabalho foi sintetizada a 13CO(15NH2)2, enriquecida em 13C e/ou 15N, a partir da reação entre 13CO, 15NH3, S e CH3OH (meio líquido), sob baixa pressão e temperatura, com simultânea produção de H2S. A reação ocorreu em reator de aço inoxidável, revestido internamente com politetrafluoretileno. Inicialmente, adicionou-se S no interior do reator. Na sequência, esse foi fechado e, sob pressão reduzida (10-3 MPa) e temperatura de 4 ºC, transferiu-se o CH3OH, H2S, 15NH3 e 13CO. Logo após, o reator foi colocado em um sistema de aquecimento (100 ºC), sob agitação mecânica. Ao final do tempo de reação (150 min.), desligou-se o aquecimento e o reator foi resfriado (± 25 ºC). Os gases resultantes do processo de síntese como 15NH3 e H2S foram recuperados em soluções de H2SO4 e outra com H2O2:NaOH. Em seguida, abriu-se o reator e removeu-se a mistura (13CO(15NH2)2, CH3OH e S) que foi submetida a procedimentos (filtração à vácuo, purificação química (CH3COCH3) e física (resinas catiônica e aniônica) para retirada de impurezas. Após, a 13CO(15NH2)2 foi cristalizada (50 ºC) e realizaram-se análises físico-químicas (teor (%) de N, ponto de fusão (ºC), teor (%) de biureto, análise multielementar (mg/kg)), microbiológicas (bactérias, fungos e leveduras) e isotópicas (% em átomos de 13C e/ou 15N). No entanto, as análises isotópicas foram realizadas em um espectrômetro de massas ATLAS-MAT, modelo CH4 (determinações absolutas), com admissão de amostras já convertida na forma gasosa. Desta forma, a obtenção do 13CO2 e 15N2 foi realizada utilizando o método via seca, onde a amostra de 13CO(15NH2)2 foi oxidada com CuO à 550 ºC em tubos de vidro (borossilicato), sob vácuo. Em seguida, os gases (15N2, 13CO2 e H2O), foram conduzidos por uma linha sob baixa pressão (10-3 MPa), acoplada on line ao sistema de admissão do espectrômetro. Esse procedimento tem a finalidade de eliminar as impurezas (interferências isobáricas) e vapor de H2O, utilizando-se da criogenia, admitindo-se o 13CO2 e/ou 15N2 ao espectrômetro para análise. Com o sistema proposto, envolvendo a reação entre 15NH3, 13CO e S (6.13, 1,12 e 1,28 g, respectivamente), tendo ainda, 40 mL de CH3OH e 40 mg de H2S, foi possível obter, em média, 1,96 g de 13CO(15NH2)2 (rendimento de 81,97 %). O processo completo, por batelada, demanda um tempo de oito a doze horas de trabalho, dependendo da fonte isotópica. A 13CO(15NH2)2 sintetizada apresentou boa qualidade físico-química (46,2 % de N, ponto de fusão de 132,5 ºC, 0,55 % de biureto e teor (mg/kg) de elementos abaixo da concentração permitida pelo órgão fiscalizador) e microbiológica (< 10 UFC/g para bactéria, fungos e leveduras). Os resultados obtidos das determinações isotópicas de N e/ou C (% em átomos de 15N e/ou 13C) indicam a viabilidade do método analítico, não sendo verificada interferência nos níveis isotópicos. A utilização do sistema on line acoplado ao espectrômetro de massa proporcionou maior velocidade analítica e facilidade no preparo das amostras para determinação isotópica de C e/ou N. Ainda os custos de produção da 13CO(15NH2)2, enriquecida em 13C e/ou 15N, mostraram-se competitivo com os valores (preço FOB) de comercialização no mercado internacional / In the present work 13CO(15NH2)2 was synthesized from 13CO, 15NH3, S and CH3OH reaction, at low pressure and temperature, with simultaneous H2S production. The reaction proceeded in a stainless steel reactor, internally lined with polytetrafluoroethylene. Initially, S was added to the reactor and, after its shutting, under reduced pressure (10-3 MPa) and 4 °C, CH3OH, H2S, 15NH3 and 13CO were shifted. The reactor was placed in a heating system (100 °C), under magnetic stirring. At the end of the reaction (150 minutes), the heating was turned off and the reactor was cooled (± 25 °C). The resulting synthesis gases, like 15NH3 and H2S, were recovered in H2SO4 and H2O2:NaOH solutions. The mixture (13CO(15NH2)2, CH3OH and S) was removed and subjected to processes for removal of impurities (vacuum filtration, chemical and physical purification (CH3COCH3 and cationic and anionic resins, respectively)). The 13CO(15NH2)2 was crystallized (50 °C) and physico-chemical (N content (%), melting point (°C), biuret content (%), multielemental analysis (mg kg-1)), microbiological (bacteria, fungi and yeasts) and isotopic (13C and/or 15N atoms %) analyses were carried out. The 13C and/or 15N analyses were performed using an ATLAS MAT-CH4 mass spectrometer (absolute determinations), with converted samples admission into gaseous form. Thus, 13CO2, and 15N2 was obtained through dry process, where 13CO(15NH2)2 sample was oxidized with CuO at 550 ºC in borosilicate glass tubes, under vacuum. The gases (15N2, 13CO2 and H2O) were led by a line under low pressure (10-3 MPa), on-line coupled with the intake system of the mass spectrometer. This procedure aimed to eliminate impurities (isobaric interferences) and H2O vapor, using cryogenics, admitting 13CO2 and 15N2 into the spectrometer for analysis. With the proposed system, involving the reaction among 15NH3, 13CO and S (6.13, 1.12 and 1.28 g, respectively), and further 40 mL of CH3OH and 40 mg of H2S was possible to obtain, on average, 1.96 g of 13CO(15NH2)2 (81.97 % of yield). The entire process, in batches, demands eight to twelve hours, depending on the isotopic source. The 13CO(15NH2)2 showed good physico-chemical (46,2 % of N, 132,5 ºC of melting point, 0,55 % of biuret and elements content (mg kg-1) lower than acceptable limits by legislation) and microbiological quality (< 10 CFU g-1 for bacteria, fungi and yeasts). The results of 15N and/or 13C isotopic determinations indicated the feasibility of the analytical method, with no isotopic level interference. The use of the on-line system coupled with mass spectrometry provided greater analytical speed and ease of sample preparation. The production costs of 13CO(15NH2)2 were competitive with FOB values in the international market