Caracterização de compósitos Nb-20%cu obtidos por moagem de alta energia e sinterizados por fase líquida

In this work, was studied the formation of a composite of the refractory metal niobium with copper, through the process of high-energy milling and liquid phase sintering. The HEM can be used to synthesize composite powders with high homogeneity and fine size particle distribution. It may also produce the solid solubility in immiscible systems such as Nb-Cu, or extend the solubility of systems with limited solubility. Therefore, in the immiscible system Cu-Nb, the high-energy milling was successfully used to obtain the composite powder particles. Initially, the formation of composite particles during the HEM and the effect of preparation technique on the microstructure of the material was evaluated. Four loads of Nb and Cu powders containing 20%wt Cu were synthesized by MAE in a planetary type ball mill under different periods of grinding. The influence of grinding time on the metal particles is evaluated during the process by the withdrawal of samples at intermediate times of milling. After compaction under different forces, the samples were sintered in a vacuum furnace. The liquid phase sintering of these samples prepared by HEM produced a homogeneous and fine grained. The composite particles forming the sintered samples are the addition of a hard phase (Nb) with a high melting point, and a ductile phase (Cu) with low melting point and high thermal and electrical conductivities. Based on these properties, the Nb-Cu system is a potential material for many applications, such as electrical contacts, welding electrodes, coils for generating high magnetic fields, heat sinks and microwave absorbers, which are coupled to electronic devices. The characterization techniques used in this study, were laser granulometry, used to evaluate the homogeneity and particle size, and the X-ray diffraction, in the phase identification and to analyze the crystalline structure of the powders during milling. The morphology and dispersion of the phases in the composite powder particles, as well the microstructures of the sintered samples, were observed by scanning electron microscopy (SEM). Subsequently, the sintered samples are evaluated for density and densification. And finally, they were characterized by techniques of measuring the electrical conductivity and microhardness, whose properties are analyzed as a function of the parameters for obtaining the composite

Regional Diversification and Performance: Conceptualization and Competing Strategic Objectives

This dissertation comprised of three essays provides justification for the need to pursue research on multinationality and performance with a more fine-grained approach. Essay one is a conceptual response to an article written by Jean-Francois Hennart in 2011 which questions the need and approach toward future research in this domain. I argue that internalization theory does not render multinationality and performance research meaningless and identify key areas where methodological enhancements can be made to strengthen our research findings with regard to Hennart’s call for more content validity. Essay two responds to the need for more-fine grained research on the consequences of multinationality by introducing non-traditional measures of performance such as social and environmental performance and adopting a more theoretically relevant construct of regionalization to capture international diversification levels of the firm. Using data from the world’s largest 600 firms (based on sales) derived from Bloomberg and the Directory of Corporate Affiliates; I employ general estimating equation analysis to account for the auto-correlated nature of the panel data alongside multivariate regression techniques. Results indicate that regionalization has a positive relationship with economic performance while it has a negative relationship with environmental and social performance outcomes, often referred to as the “Triple Bottom-Line” performance. Essay three builds upon the work in the previous essays by linking the aforementioned performance variables and sample to corporate reputation which has been shown to be a beneficial strategic asset. Using Structural Equation Modeling I explore economic, environmental and social signals as mediators on relationship between regionalization and firm reputation. Results indicate that these variables partially mediate a positive relationship between regionalization and firm reputation. While regionalization positively affects the reputation building signal of economic performance, it aids in reputation building by reducing environmental and social disclosure effects which interestingly impact reputation negatively. In conclusion, the dissertation submits opportunities for future research and contributes to research by demonstrating that regionalization affects performance, but the effect varies in accordance with the performance criterion and context. In some cases, regional diversification may produce competing or conflicting outcomes among the potential strategic objectives of the firm.

Impact of single parameter changes on Ceph cloud storage performance

In a general purpose cloud system efficiencies are yet to be had from supporting diverse applications and their requirements within a storage system used for a private cloud. Supporting such diverse requirements poses a significant challenge in a storage system that supports fine grained configuration on a variety of parameters. This paper uses the Ceph distributed file system, and in particular its global parameters, to show how a single changed parameter can effect the performance for a range of access patterns when tested with an OpenStack cloud system.

When do dialects become languages? A cognitive perspective

Several definitions exist that offer to identify the boundaries between languages and dialects, yet these distinctions are inconsistent and are often as political as they are linguistic (Chambers & Trudgill, 1998). A different perspective is offered in this thesis, by investigating how closely related linguistic varieties are represented in the brain and whether they engender similar cognitive effects as is often reported for bilingual speakers of recognised independent languages, based on the principles of Green’s (1998) model of bilingual language control. Study 1 investigated whether bidialectal speakers exhibit similar benefits in non-linguistic inhibitory control as a result of the maintenance and use of two dialects, as has been proposed for bilinguals who regularly employ inhibitory control mechanisms, in order to suppress one language while speaking the other. The results revealed virtually identical performance across all monolingual, bidialectal and bilingual participant groups, thereby not just failing to find a cognitive control advantage in bidialectal speakers over monodialectals/monolinguals, but also in bilinguals; adding to a growing body of evidence which challenges this bilingual advantage in non-linguistic inhibitory control. Study 2 investigated the cognitive representation of dialects using an adaptation of a Language Switching Paradigm to determine if the effort required to switch between dialects is similar to the effort required to switch between languages. The results closely replicated what is typically shown for bilinguals: Bidialectal speakers exhibited a symmetrical switch cost like balanced bilinguals while monodialectal speakers, who were taught to use the dialect words before the experiment, showed the asymmetrical switch cost typically displayed by second language learners. These findings augment Green’s (1998) model by suggesting that words from different dialects are also tagged in the mental lexicon, just like words from different languages, and as a consequence, it takes cognitive effort to switch between these mental settings. Study 3 explored an additional explanation for language switching costs by investigating whether changes in articulatory settings when switching between different linguistic varieties could - at least in part – be responsible for these previously reported switching costs. Using a paradigm which required participants to switch between using different articulatory settings, e.g. glottal stops/aspirated /t/ and whispers/normal phonation, the results also demonstrated the presence of switch costs, suggesting that switching between linguistic varieties has a motor task-switching component which is independent of representations in the mental lexicon. Finally, Study 4 investigated how much exposure is needed to be able to distinguish between different varieties using two novel language categorisation tasks which compared German vs Russian cognates, and Standard Scottish English vs Dundonian Scots cognates. The results showed that even a small amount of exposure (i.e. a couple of days’ worth) is required to enable listeners to distinguish between different languages, dialects or accents based on general phonetic and phonological characteristics, suggesting that the general sound template of a language variety can be represented before exact lexical representations have been formed. Overall, these results show that bidialectal use of typologically closely related linguistic varieties employs similar cognitive mechanisms as bilingual language use. This thesis is the first to explore the cognitive representations and mechanisms that underpin the use of typologically closely related varieties. It offers a few novel insights and serves as the starting point for a research agenda that can yield a more fine-grained understanding of the cognitive mechanisms that may operate when speakers use closely related varieties. In doing so, it urges caution when making assumptions about differences in the mechanisms used by individuals commonly categorised as monolinguals, to avoid potentially confounding any comparisons made with bilinguals.

Tracing outsideness: young women's institutional journeys and the geographies of closed space

Understanding confinement and its complex workings between individuals and society has been the stated aim of carceral geography and wider studies on detention. This project contributes ethnographic insights from multiple sites of incarceration, working with an under-researched group within confined populations. Focussing on young female detainees in Scotland, this project seeks to understand their experiences of different types of ‘closed’ space. Secure care, prison and closed psychiatric facilities all impact on the complex geographies of these young women’s lives. The fluid but always situated relations of control and care provide the backdrop for their journeys in/out and beyond institutional spaces. Understanding institutional journeys with reference to age and gender allows an insight into the highly mobile, often precarious, and unfamiliar lives of these young women who live on the margins. This thesis employs a mixed-method qualitative approach and explores what Goffman calls the ‘tissue and fabric’ of detention as a complex multi-institutional practice. In order to be able to understand the young women’s gendered, emotional and often repetitive experiences of confinement, analysis of the constitution of ‘closed space’ represents a first step for inquiry. The underlying nature of inner regimes, rules and discipline in closed spaces, provide the background on which confinement is lived, perceived and processed. The second part of the analysis is the exploration of individual experiences ‘on the inside’, ranging from young women’s views on entering a closed institution, the ways in which they adapt or resist the regime, and how they cope with embodied aspects of detention. The third and final step considers the wider context of incarceration by recovering the young women’s journeys through different types of institutional spaces and beyond. The exploration of these journeys challenges and re-develops understandings of mobility and inertia by engaging the relative power of carceral archipelagos and the figure of femina sacra. This project sits comfortably within the field of carceral geography while also pushing at its boundaries. On a conceptual level, a re-engagement with Goffman’s micro-analysis challenges current carceral-geographic theory development. Perhaps more importantly, this project pushes for an engagement with different institutions under the umbrella of carceral geography, thus creating new dialogues on issues like ‘care’ and ‘control’. Finally, an engagement with young women addresses an under-represented population within carceral geography in ways that raise distinctly problematic concerns for academic research and penal policy. Overall, this project aims to show the value of fine grained micro-level research in institutional geographies for extending thinking and understanding about society’s responses to a group of people who live on the margins of social and legal norms.

Design and Development of Network Monitoring Strategies in P4-enabled Programmable Switches

Network monitoring is of paramount importance for effective network management: it allows to constantly observe the network’s behavior to ensure it is working as intended and can trigger both automated and manual remediation procedures in case of failures and anomalies. The concept of SDN decouples the control logic from legacy network infrastructure to perform centralized control on multiple switches in the network, and in this context, the responsibility of switches is only to forward packets according to the flow control instructions provided by controller. However, as current SDN switches only expose simple per-port and per-flow counters, the controller has to do almost all the processing to determine the network state, which causes significant communication overhead and excessive latency for monitoring purposes. The absence of programmability in the data plane of SDN prompted the advent of programmable switches, which allow developers to customize the data-plane pipeline and implement novel programs operating directly in the switches. This means that we can offload certain monitoring tasks to programmable data planes, to perform fine-grained monitoring even at very high packet processing speeds. Given the central importance of network monitoring exploiting programmable data planes, the goal of this thesis is to enable a wide range of monitoring tasks in programmable switches, with a specific focus on the ones equipped with programmable ASICs. Indeed, most network monitoring solutions available in literature do not take computational and memory constraints of programmable switches into due account, preventing, de facto, their successful implementation in commodity switches. This claims that network monitoring tasks can be executed in programmable switches. Our evaluations show that the contributions in this thesis could be used by network administrators as well as network security engineers, to better understand the network status depending on different monitoring metrics, and thus prevent network infrastructure and service outages.

Hybrid Artificial Intelligence to Extract Patterns and Rules from Argumentative and Legal Texts

This Thesis is composed of a collection of works written in the period 2019-2022, whose aim is to find methodologies of Artificial Intelligence (AI) and Machine Learning to detect and classify patterns and rules in argumentative and legal texts. We define our approach “hybrid”, since we aimed at designing hybrid combinations of symbolic and sub-symbolic AI, involving both “top-down” structured knowledge and “bottom-up” data-driven knowledge. A first group of works is dedicated to the classification of argumentative patterns. Following the Waltonian model of argument and the related theory of Argumentation Schemes, these works focused on the detection of argumentative support and opposition, showing that argumentative evidences can be classified at fine-grained levels without resorting to highly engineered features. To show this, our methods involved not only traditional approaches such as TFIDF, but also some novel methods based on Tree Kernel algorithms. After the encouraging results of this first phase, we explored the use of a some emerging methodologies promoted by actors like Google, which have deeply changed NLP since 2018-19 — i.e., Transfer Learning and language models. These new methodologies markedly improved our previous results, providing us with best-performing NLP tools. Using Transfer Learning, we also performed a Sequence Labelling task to recognize the exact span of argumentative components (i.e., claims and premises), thus connecting portions of natural language to portions of arguments (i.e., to the logical-inferential dimension). The last part of our work was finally dedicated to the employment of Transfer Learning methods for the detection of rules and deontic modalities. In this case, we explored a hybrid approach which combines structured knowledge coming from two LegalXML formats (i.e., Akoma Ntoso and LegalRuleML) with sub-symbolic knowledge coming from pre-trained (and then fine-tuned) neural architectures.

Data sensitivity detection in chat interactions for privacy protection

In recent years, there has been exponential growth in using virtual spaces, including dialogue systems, that handle personal information. The concept of personal privacy in the literature is discussed and controversial, whereas, in the technological field, it directly influences the degree of reliability perceived in the information system (privacy ‘as trust’). This work aims to protect the right to privacy on personal data (GDPR, 2018) and avoid the loss of sensitive content by exploring sensitive information detection (SID) task. It is grounded on the following research questions: (RQ1) What does sensitive data mean? How to define a personal sensitive information domain? (RQ2) How to create a state-of-the-art model for SID?(RQ3) How to evaluate the model? RQ1 theoretically investigates the concepts of privacy and the ontological state-of-the-art representation of personal information. The Data Privacy Vocabulary (DPV) is the taxonomic resource taken as an authoritative reference for the definition of the knowledge domain. Concerning RQ2, we investigate two approaches to classify sensitive data: the first - bottom-up - explores automatic learning methods based on transformer networks, the second - top-down - proposes logical-symbolic methods with the construction of privaframe, a knowledge graph of compositional frames representing personal data categories. Both approaches are tested. For the evaluation - RQ3 – we create SPeDaC, a sentence-level labeled resource. This can be used as a benchmark or training in the SID task, filling the gap of a shared resource in this field. If the approach based on artificial neural networks confirms the validity of the direction adopted in the most recent studies on SID, the logical-symbolic approach emerges as the preferred way for the classification of fine-grained personal data categories, thanks to the semantic-grounded tailor modeling it allows. At the same time, the results highlight the strong potential of hybrid architectures in solving automatic tasks.

Serverless middlewares to integrate heterogeneous and distributed services in cloud continuum environments

The application of modern ICT technologies is radically changing many fields pushing toward more open and dynamic value chains fostering the cooperation and integration of many connected partners, sensors, and devices. As a valuable example, the emerging Smart Tourism field derived from the application of ICT to Tourism so to create richer and more integrated experiences, making them more accessible and sustainable. From a technological viewpoint, a recurring challenge in these decentralized environments is the integration of heterogeneous services and data spanning multiple administrative domains, each possibly applying different security/privacy policies, device and process control mechanisms, service access, and provisioning schemes, etc. The distribution and heterogeneity of those sources exacerbate the complexity in the development of integrating solutions with consequent high effort and costs for partners seeking them. Taking a step towards addressing these issues, we propose APERTO, a decentralized and distributed architecture that aims at facilitating the blending of data and services. At its core, APERTO relies on APERTO FaaS, a Serverless platform allowing fast prototyping of the business logic, lowering the barrier of entry and development costs to newcomers, (zero) fine-grained scaling of resources servicing end-users, and reduced management overhead. APERTO FaaS infrastructure is based on asynchronous and transparent communications between the components of the architecture, allowing the development of optimized solutions that exploit the peculiarities of distributed and heterogeneous environments. In particular, APERTO addresses the provisioning of scalable and cost-efficient mechanisms targeting: i) function composition allowing the definition of complex workloads from simple, ready-to-use functions, enabling smarter management of complex tasks and improved multiplexing capabilities; ii) the creation of end-to-end differentiated QoS slices minimizing interfaces among application/service running on a shared infrastructure; i) an abstraction providing uniform and optimized access to heterogeneous data sources, iv) a decentralized approach for the verification of access rights to resources.

Oxidative potential for fine/ultrafine particles in occupational situations

Introduction : The redox properties of fine/ultrafine particles as well as nanoparticles (NP) are suggested to be important to explain their biological activity and could constitute a novel and promising metric for hazard evaluation. The acellular in vitro dithiothreitol (DTT) assay allows measuring this property. Objectives : (1) to evaluate sampling requirements for fine/ultrafine particle allowing measurement of their oxidative potential (2) to apply the methodology to occupational situations where particle from combustion sources are generated. Material and method : Sampling parameters (type of filters and loaded amount) and storage duration affecting the DTT measurements were evaluated. Based on these results, a methodological approach was defined and applied in two occupational situations where diesel and other combustion particles are present (toll station in a tunnel and mechanical yard for bus reparation). Results : Teflon filters loaded with diesel particles were found more suitable for the DTT assay, due to their better chemical inertness compared to quartz filters: after storage durations larger than 150 hours, an increased reactivity toward DTT was observed only with quartz filters. Reactivity was linearly correlated to the loaded mass until about 1000 μg/filter. Different redox reactivities were determined in both working places, with the mechanical yard presenting a higher DTT consumption rate. Discussion and conclusions : These results demonstrate the feasibility of this method to determine the oxidative potential of fine/ultrafine particles in occupational situations. We propose to include this approach for hazard assessment of work places with exposure to manufactured and other NP.

Elemental and isotopic zoning in natural alpine quartz

THESIS ABSTRACT : Stable isotope geochemistry is used to help resolve a large number of geological questions. In order to do this, it is essential to understand the different mechanisms that govern isotopic fractionation processes between different phases and to identify the conditions required to reach equilibrium fractionation. However, at low temperatures, these processes are poorly constrained and many factors can induce differential partitioning of the isotopes between sectors of a mineral species and the fluid during mineral growth. This can result in so-called 'sector zoning' of a mineral species. The aim of this thesis is to evaluate the occurrence of sector zoning of the oxygen isotopes and trace elements in natural α-quartz crystals and to identify the reasons for such zoning. The implications for the fluid-mineral interactions are studied in the context of the Alpine metamorphism. The approach chosen has focused on examining the crystal structure, cathodoluminescence appearance (CL), and on relating elemental (e.g. Li, Na, Al, P, K, Ca, Ge, Ti, Fe) to stable oxygen isotope compositions between and along different growth sectors. Low temperature quartz samples were selected from Alpine veins in different localities, where growth conditions have already been well constrained. The mineralogy as well as the isotopic compositions of the host rocks were also investigated, in order to interpret the variations obtained between the different growth stages in the framework of fluid-rock interaction during Alpine metamorphism. Depending on the growth conditions, most of the studied quartz is strongly zoned in CL, and it reveals corresponding zonations in the trace element content (e.g. growth zoning). Aluminium, substituting for Si in the lattice, was found in concentrations up to 1000's ppma, and its distribution is strongly related to Li and H and to a lesser extent, to Ge. Elemental sector zoning is evident from the distribution of these three elements since they exhibit differences in their respective concentrations between faces for distinct growth zones, with prismatic faces having the lowest Al contents. Quartz from veins in magmatic rocks, for example, tend to have lower Al concentrations and similar concentrations of Li and Ti suggesting also a contribution of these elements from the host rock. The relationship between Al and Li is still correlated. Only Alpine crystals grown at higher temperatures (~400°C) without any CL zoning feature are free of these impurities and do not show such zoning characteristics. Differences in the δ18O values were measured between different faces principally in the AIenriched growth zones or stages. These results were confirmed by the means of two different methods (in situ/non in situ). However, it was determined that the Al concentrations do not affect significantly oxygen isotope fractionations at 300°C. The results altogether suggest that the presence of sector zoning in quartz crystals is real, but not universal, and henceforth should be taken into consideration for any use of these systems. The occurrence of disequilibrium partitioning has been enhanced and is possibly related to kinetic processes as well as structural effects that do not affect similarly trace element incorporation and isotopic fractionation. In situ measurements also revealed fine scale δ18O zonations along growth paths that are useful to constrain fluid-rock interactions during Alpine metamorphism. Variations in the δ18O values present along growth vectors indicate changes in the fluid composition and origin. Association with oxygen isotope composition of the host rock allows for the deduction of interactions between rocks, veins and consequently fluids, as well as fluid regimes. RESUME DE LA THESE : A basses températures, (i.e. <400°C) les différents mécanismes qui régissent le fractionnement isotopique ainsi que les conditions nécessaires pour établir un état d'équilibre sont peu connus et nombre de paramètres peuvent entraîner un partitionnement chimique différentiel entre différents secteurs d'un minéral et le fluide en contact. Ainsi, ce travail de thèse a pour but d'évaluer la possible présence de zonages sectoriels en isotopes de l'oxygène mais aussi en éléments traces dans des cristaux naturels de quartz-α de basses températures, ainsi que les raisons d'un tel phénomène et enfin ses implications sur les interactions fluide-roche, principalement dans le cadre du métamorphisme Alpin. La structure et l'apparence en cathodoluminescence (CL) des échantillons ont été caractérisées avant de retracer en détail les compositions en élément traces (Li, Na, Al, P, K, Ca, Ge, Ti, Fe) et en isotopes de l'oxygène, le long et entre différents secteurs. Les échantillons de quartz sélectionnés proviennent majoritairement de veines Alpine de différentes localités, où les conditions de croissance ont été déjà bien caractérisées. Les compositions minéralogiques et isotopiques de la roche encaissante ont aussi été examinées, pour contraindre les variations obtenues dans un contexte Alpin. Selon leurs conditions de croissance, la plupart des cristaux étudiés sont fortement zonés, ce qui est souligné par un zonage des concentrations en éléments traces (e.g. zonage de croissance). L'Aluminium, qui peut se substituer à la Silice dans le réseau cristallin, a été retrouvé jusqu'en très grandes concentrations dans certaines zones (plusieurs milliers de ppma). De plus, la distribution en Al est fortement liée à celles de Li et H, ainsi que dans une moindre mesure à Ge. La présence de zonage sectoriel est évidente au niveau de ces éléments qui montrent de larges différences de concentrations entre différentes faces pour une même zone de croissance, avec les concentrations les plus basses retrouvées dans les faces prismatiques. Les quartz de veines situées dans des roches magmatiques par exemple possèdent des concentrations en Li et Ti de même ordre de grandeur, confirmant le rôle de la composition de la roche encaissante. La relation Li/Al est toujours fortement présente, mais ce rapport est fonction de la face mesurée. Seuls les cristaux Alpins de plus hautes températures (400°C) ne possédant pas de zones en CL ne présentent aucune de ces caractéristiques. Des différences dans les valeurs de δ18O de zones identiques enrichies en Al ont clairement été mesurées entre les différentes faces r, z, et m, mais aussi au sein d'une même seule zone, indiquant que le fractionnement a probablement eu lieu en déséquilibre. Il a été déterminé que la présence d'Al dans ces teneurs n'avait qu'un faible effet sur le fractionnement isotopique de l'oxygène. L'utilisation de deux méthodes différentes a permis d'obtenir des résultats in situ et non in situ concordants. La comparaison des résultats obtenus permet de démontrer que le zonage sectoriel est bien présent dans certains cristaux de quartz, et dépend des conditions de formation. La présence d'un partitionnement différentiel des éléments traces peut être due à des effets cinétiques aussi bien que structuraux, alors que le zonage sectoriel des isotopes de l'oxygène aurait d'autres origines. Il est alors évident que la possibilité de zonage sectoriel doit être désormais pris en considération avant toute interprétations de données isotopiques de cristaux zonés. Les mesures in situ ont de plus permis de distinguer de fines variations des valeurs δ18O au cours de la croissance, qui peuvent aider à retracer la circulations des fluides dans les Alpes durant cette période. En association avec les compositions des roches encaissantes, ii est possible de déduire les interactions entre roches, veines, et par conséquent fluides, au cours de différentes étapes. RESUME GRAND PUBLIC : La géochimie des isotopes stables a pris beaucoup d'importance depuis ces dernières années pour aider à résoudre nombre de questions géologiques, en se basant sur les caractéristiques du fractionnement isotopiques pour différents systèmes. Il est donc nécessaire d'avoir une connaissance approfondie des mécanismes qui s'appliquent au fractionnement isotopique entre les minéraux et les fluides à partir desquels ils se forment. Ces mécanismes ont été bien approchés par différents types de calibrations pour des systèmes à hautes températures, cependant cela n'est pas aussi évident pour les systèmes à des températures inférieures à 400-500°C. Ce travail de thèse a pour but d'aider à la description et la compréhension des phénomènes qui peuvent affecter le fractionnement isotopique à basses températures, ainsi que leurs implications, à partir de l'étude de cristaux de quartz. Le choix des échantillons s'est porté sur des cristaux naturels formés à des températures inférieures ou égales à 400°C, provenant majoritairement de fissures hydrothermales Alpines dont les conditions de formation ont déjà été déterminées. L'étude des cristaux Alpin permet de plus de replacer les résultats obtenus dans le contexte du métamorphisme Alpin au cours du Miocène (21-13 Ma). Après examen de la structure et de la morphologie des cristaux, et leur caractérisation par cathodoluminescence (CL), des analyses chimiques détaillées sur les éléments en traces pouvant entrer dans le réseau cristallin du quartz comme impuretés (i.e. Li, Na, Al, P, K, Ca, Ge, Ti), et des isotopes stables de l'oxygène, ont été menées. En fonction des conditions de croissance, la plupart des cristaux présentent des zonations, qui peuvent être facilement reliées à la distribution des éléments traces analysés par microsonde électronique, sonde ionique (SIMS) et LA-ICPMS. De fortes concentrations d'Aluminium (plusieurs milliers de parties par million atomique) ont pu être observées dans les zones les plus externes des cristaux. De plus, les concentrations en Al et en Li sont toujours corrélées; la présence d'Hydrogène déduite à partir d'analyses par FTIR suit cette même tendance. Les différentes faces des cristaux présentent des concentrations distinctes d'Al, Li et H pour des mêmes zones de croissance, avec par exemple les concentrations les plus faibles dans les zones des faces prismatiques. Cela implique la présence d'un zonage sectoriel, qui a déjà été observé principalement dans des carbonates mais jamais décrit auparavant pour des quartz. Seuls les cristaux alpins homogènes en CL dont la croissance s'est faite à plus haute température (400°C) ne présentent aucune de ces caractéristiques. Par analogie avec le zonage sectoriel en Al, élément qui se substitue au Si dans le réseau cristallin du quartz, il est possible de penser qu'un zonage sectoriel pourrait aussi s'appliquer aux isotopes de l'oxygène. Des précédentes études avaient en effet émis cette hypothèse. Nos résultats ont été obtenus à partir d'analyses à la fois in- situ par SIMS, et par extraction assistée par laser-CO2 sur des parties de quartz soigneusement séparées, et sont en accord entre les deux méthodes. Un zonage sectoriel est en effet bien présent pour les cristaux alpins, mais principalement au niveau des zones très riches en Aluminium. Cependant, il a été déterminé que la présence d'Al dans ces teneurs avait un effet plus que minimal sur le fractionnement isotopique de l'oxygène. Des différences importantes ont été observées entre les faces r & z mais aussi au sein d'une même et seule zone, indiquant que le fractionnement a pu avoir lieu en déséquilibre, ce qui est aussi visible au niveau des valeurs totalement opposées entre faces pour la dernière phase de croissance de certains cristaux. Ainsi l'association de ces résultats laisse suggérer que la présence d'un zonage sectoriel peut être liée à différents paramètres tels que le taux de croissance ou la structure de surface du cristal, mais qui n'affectent pas de la même façon l'incorporation des éléments traces et le fractionnement isotopique. La possibilité d'un zonage sectoriel est importante à prendre en compte lors de toute interprétation de données isotopiques. Les analyses des isotopes de l'oxygène effectuées par SIMS ont aussi permis de distinguer des variations importantes à petite échelle au cours de la croissance. Des mesures faites par laser CO2 sur certaines roches encaissantes, ont permis distinguer plusieurs étapes dans la croissance des minéraux et de déduire le rôle de l'encaissant et le type de fluide. En association avec de précédentes études, il a été ainsi possible de mieux contraindre la formation de ces cristaux dans le contexte alpin et la circulation de fluide au cours du métamorphisme alpin durant le Miocène.

Spectral induced polarization: Laboratory measurements on sandy quartz samples of varied pore characteristics

Understanding the influence of pore space characteristics on the hydraulic conductivity and spectral induced polarization (SIP) response is critical for establishing relationships between the electrical and hydrological properties of surficial sedimentary deposits. Here, we present the results of laboratory SIP measurements on saturated quartz samples with granulometric characteristics ranging from fine sand to fine gravel. We alter the pore characteristics using three principal methods: (i) variation of the grain sizes, (ii) changing the degree of compaction, and (iii) changing the level of sorting. We then examine how these changes affect both the SIP response and the hydraulic conductivity. In general, the results indicate a clear connection between the applied changes in pore characteristics and the SIP response. In particular, we observe a systematic correlation between the hydraulic conductivity and the relaxation time of the Cole-Cole model describing the observed SIP effect for the whole range of considered grain sizes.

Caracterização geológica, geoquímica e geocronológica da suíte plutônica enoproterozóica da região de Serrinha, porção centro-leste do maciço São José de Campestre, sudeste do RN

The of Serrinha plutonic suite, northeastern portion of the Borborema Province (NE Brazil), is characterized by a voluminous and diversified magmatism of Neoproterozoic age, intrusive in the Archean to Paleoproterozoic gneissic-migmatitic basement of the São José de Campestre massif. Field relations and petrographic and geochemical data allowed us to individualize different lithologic types among this plutonic suite, which is represented by intermediate to mafic enclaves, porphyritic diorites, porphyritic granitoids, porphyritic granodiorites, microporphyritic granites and dykes/sheets of microgranite. The intermediate-to-mafic enclaves occur associated with porphyritic granitoids, showing mixture textures. The porphyrytic diorites occur as isolated bodies, generally associated with intermediate-to-mafic enclaves and locally as enclaves within porphyritic granites. The granodiorites represent mixing between an intermediate to mafic magma with an acidic one. The micropophyritic granites occur as isolated small bodies, generally deformed, while the microgranite dykes/sheets crosscut all the previous granitoids. A U-Pb zircon age of 576 + 3 Ma was obtained for the Serrinha granite. This age is interpreted as age of the peak of the regional ductile deformational event (D3) and of the associated the E-W Rio Jacu shear zone, which control the emplacement of the Neoproterozoic syntectonic plutons. The porphyrytic granitoids show monzogranitic composition, transitional between peraluminous and metaluminous types, typically of the high potassium subalkaline-calc-alkaline series. The intermediate-to-mafic enclaves present vary from quartz diorite to tonalite/granodiorite, with metaluminous, shoshonitic affinity. The diorites are generally quartz-monzodiorite in composition, with metaluminous, subalkaline affinity. They display coarse-grained, inequigranular, porphyrytic texture, with predominance of plagioclase phenocrystals immersed in a matrix composed of biotite and pyroxenes. The microporphyrytic granites are essentially monzogranites of fine- to medium-grained texture, whereas microgranite dikes/sheets varying from monzogranites to syenogranites, with fine to media texture, equigranular. The diversified magmatism occurring at a relatively small surface associated with shear zones, suggests lithospheric dimensions for such structures, with magma extractions from different depths within the lower crust and upper mantle. The geological, geochemical and geochronological characteristics of the Serrinha plutonic suite suggest a pos-collisional geodynamic context for the Neoproterozoic magmatism. Thermobarometric data show emplacement conditions in the range 5-6 kbar (AlTamphibole) and 730-740°C (plagioclase-amphibole) for the porphyrytic granitoids (Serrinha body) and the intermediate-to-mafic enclaves

Camadas de tempestito grosso (coarse grained storm beds): exemplos do Permiano da bacia do Paraná

Tempestitos grossos constituem camadas delgadas de conglomerado gradando a arenito, com estratificação cruzada seguida de laminação ondulada truncante a simétrica e de drape/flaser de siltito/folhelho. Cinco exemplos extraídos do Permiano da bacia do Paraná ilustram esse tipo de depósito: três deles são de rochas siliciclásticas, contendo bioclastos de bivalves e vertebrados (Formação Rio Bonito-Membro Triunfo e Formação Palermo), enquanto os outros dois são de rochas carbonática e fosfática (respectivamente, formações Teresina e Corumbataí do Grupo Passa Dois). O componente tracional da base do tempestito grosso apresenta-se como arenite quartzoso/lítico ou grainstone oolítico com cimento calcífero preenchendo poros (casos das formações Palermo e Teresina). em sua maioria, os tempestitos grossos constituem pavimentos transgressivos intercalados em folhelhos ou tempestitos finos (arenitos muito finos a folhelhos com estratificação ondulada truncante-hummocky). em outro caso, extraído de subsuperfície, o pavimento transgressivo ocorre na base de uma sucessão progradante de barra de plataforma. O tempestito grosso da Formação Teresina constitui um evento transgressivo sobreposto a depósitos de barra de plataforma.

Burial history and porosity evolution of Brazilian upper Jurassic to tertiary sandstone reservoirs

The parameter time-depth index (TDI) is applied in this study to quantify empirically the influence of burial history on sandstone porosity evolution. The TDI, expressed in kilometers per million years of age, is defined as the area in the burial history diagram enclosed by the burial curve of the reservoir and the axes of the diagram. In practice, reservoir depths during burial history are integrated at regular time intervals of 1 m.y. The calculations exclude present-day bathymetry or paleobathymetry. Sandstone reservoirs from several sedimentary basins along the Brazilian continental margin (Santos, Campos, Espírito Santo, Cumuruxatiba, Recôncavo, Sergipe, Alagoas, and Potiguar) were analyzed to investigate the evolution of porosity against TDI. These Upper Jurassic to Tertiary sandstones lie in depths of 700 to 4900 m, and are hydrocarbon charged (oil or gas). Average porosities of most of these reservoirs were obtained from core analysis, and a few porosity data were taken from well log interpretations. Detrital constituents of the sandstones are mainly quartz, feldspar, and granitic/gneissic rock fragments. Sandstones were grouped into three main reservoir types, based on composition (detrital quartz content) and grain sorting: Type I (average quartz content <50%) are very coarse grained to conglomeratic, poorly to very poorly sorted lithic arkoses. Rock fragments are mainly granitic/gneissic and coarse grained. Type II (average quartz content ranging from 50% to 70%) are fine- to coarse-grained (pebbles absent or occurring in small percentages), moderately sorted arkoses. Type III (average quartz content >80%) are fine to coarse, moderately to poorly sorted quartz arenites or subarkoses. Plots of average porosity against depth show great dispersion in porosity values; such dispersion is mostly due to differences in the reservoir burial histories. However, plotting porosity values against the TDI for individual reservoir types produces well-defined trends. The decrease in porosity is less marked in Type III reservoirs, intermediate in Type II, and faster in Type I. Such plots suggest that it is possible to make relatively accurate porosity predictions based on reservoir TDI, texture, and composition,: within the constraints of reservoir depth/age and basin tectonics analyzed in this study.