Water–montmorillonite systems: Neutron scattering and tracer throughdiffusion studies

Designs for deep geological respositories of nuclear waste include bentonite as a hydraulic and chemisorption buffer material to protect the biosphere from leakage of radionuclides. Bentonite is chosen because it is a cheap, naturally occurring material with the required properties. It consists essentially of montmorillonite, a swelling clay mineral. Upon contact with groundwater such clays can seal the repository by incorporating water in the interlayers of their crystalline structure. The intercalated water exhibits significantly different properties to bulk water in the surrounding interparticle pores, such as lower diffusion coefficients (González Sánchez et. al. 2008). This doctoral thesis presents water distribution and diffusion behavior on various time and space scales in montmorillonite. Experimental results are presented for Na- and Cs-montmorillonite samples with a range of bulk dry densities (0.8 to 1.7 g/cm3). The experimental methods employed were neutron scattering (backscattering, diffraction, time-of-flight), adsorption measurements (water, nitrogen) and tracer-through diffusion. For the tracer experiments the samples were fully saturated via the liquid phase under volume-constrained conditions. In contrast, for the neutron scattering experiments, the samples were hydrated via the vapor phase and subsequently compacted, leaving a significant fraction of interparticle pores unfilled with water. Owing to these differences in saturation, the water contents of the samples for neutron scattering were characterized by gravimetry whereas those for the tracer experiments were obtained from the bulk dry density. The amount of surface water in interlayer pores could be successfully discriminated from the amount of bulk-like water in interparticle pores in Na- and Csmontmorillonite using neutron spectroscopy. For the first time in the literature, the distribution of water between these two pore environments was deciphered as a function of gravimetric water content. The amount was compared to a geometrical estimation of the amount of interlayer and interparticle water determined by neutron diffraction and adsorption measurements. The relative abundances of the 1 to 4 molecular water layers in the interlayer were determined from the area ratios of the (001)-diffraction peaks. Depending on the characterization method, different fractions of surface water and interlayer water were obtained. Only surface and interlayer water exists in amontmorillonite with water contents up to 0.18 g/g according to spectroscopic measurements and up to 0.32 g/g according to geometrical estimations, respectively. At higher water contents, bulk-like and interparticle water also exists. The amounts increase monotonically, but not linearly, from zero to 0.33 g/g for bulk-like water and to 0.43 g/g for interparticle water. It was found that water most likely redistributes between the surface and interlayer sites during the spectroscopic measurements and therefore the reported fraction is relevant only below about -10 ºC (Anderson, 1967). The redistribution effect can explain the discrepancy in fractions between the methods. In a novel approach the fractions of water in different pore environments were treated as a fixed parameter to derive local diffusion coefficients for water from quasielastic neutron scattering data, in particular for samples with high water contents. Local diffusion coefficients were obtained for the 1 to 4 molecular water layers in the interlayer of 0.5·10–9, 0.9·10–9, 1.5·10–9 and 1.4·10–9 m²/s, respectively, taking account of the different water fractions (molecular water layer, bulk-like water). The diffusive transport of 22Na and HTO through Na-montmorillonite was measured on the laboratory experimental scale (i.e. cm, days) by tracer through-diffusion experiments. We confirmed that diffusion of HTO is independent of the ionic strength of the external solution in contact with the clay sample but dependent on the bulk dry density. In contrast, the diffusion of 22Na was found to depend on both the ionic strength of the pore solution and on the bulk dry density. The ratio of the pore and surface diffusion could be experimentally determined for 22Na from the dependence of the diffusion coefficient on the ionic strength. Activation energies were derived from the temperaturedependent diffusion coefficients via the Arrhenius relation. In samples with high bulk dry density the activation energies are slightly higher than those of bulk water whereas in low density samples they are lower. The activation energies as a function of ionic strengths of the pore solutions are similar for 22Na and HTO. The facts that (i) the slope of the logarithmic effective diffusion coefficients as a function of the logarithmic ionic strength is less than unity for low bulk dry densities and (ii) two water populations can be observed for high gravimetric water contents (low bulk dry densities) support the interlayer and interparticle porosity model proposed by Glaus et al. (2007), Bourg et al. (2006, 2007) and Gimmi and Kosakowski (2011).

Erosion in relation to nutrition and the environment.

When considering the erosive potential of a food or drink, a number of factors must be taken into account. pH is arguably the single most important parameter in determining the rate of erosive tissue dissolution. There is no clear-cut critical pH for erosion as there is for caries. At low pH, it is possible that other factors are sufficiently protective to prevent erosion, but equally erosion can progress in acid of a relatively high pH in the absence of mitigating factors. Calcium and phosphate concentration, in combination with pH, determine the degree of saturation with respect to tooth minerals. Solutions supersaturated with respect to enamel or dentine will not cause them to dissolve, meaning that given sufficient common ion concentrations erosion will not proceed, even if the pH is low. Interestingly, the addition of calcium is more effective than phosphate at reducing erosion in acid solutions. Today, several calcium-enriched soft drinks are on the market, and acidic products with high concentrations of calcium and phosphorus are available (such as yoghurt), which do not soften the dental hard tissues. The greater the buffering capacity of the drink or food, the longer it will take for the saliva to neutralize the acid. A higher buffer capacity of a drink or foodstuff will enhance the processes of dissolution because more release of ions from the tooth mineral is required to render the acid inactive for further demineralization. Temperature is also a significant physical factor; for a given acidic solution, erosion proceeds more rapidly the higher the temperature of that solution. In recent years, a number of interesting potentially erosion-reducing drink and food additives have been investigated.

Safety and tolerability of slow-release oral morphine versus methadone in the treatment of opioid dependence

Opioid substitution treatment (OST) for opioid dependence may be limited by adverse events (AEs). Increasing the range of therapeutic options optimizes outcomes and facilitates patient management. An international, multi-center, two-phase study investigated the efficacy and safety of slow-release oral morphine (SROM) versus methadone in patients receiving methadone therapy for opioid dependence. In phase 1 (two way cross-over, 11 weeks each period) patients were randomized to SROM or methadone oral solution. In phase 2 (25 weeks), patients continued treatment with SROM (group A) or switched from methadone to SROM (group B). In total, 211 out of 276 completed phase 1 and 198 entered phase 2 (n = 95 group A, n = 103 group B). Treatment with both SROM and methadone was well tolerated. However, the mean QTc-interval associated with methadone was significantly longer than that under SROM. Higher treatment satisfaction, fewer cravings for heroin, and lower mental stress were reported with SROM. This study adds a significant further weight of evidence that SROM is an effective and well tolerated long-term maintenance treatment for opioid dependence with a beneficial risk profile compared to methadone regarding cardiac effects and supports its clinical utility.

Four years follow-up after clavicle reconstruction in a child: a case report.

Clavicle reconstruction is a rare operation. In most cases a mid-shaft defect of the clavicle is bridged by using different grafting techniques or musculo-osteous flaps. In some clinical situations where reconstruction is not a suitable option claviculectomy as a salvation procedure has proven to be an acceptable solution. In the paediatric population the challenge of both the cosmetic and the functional result attempting reconstruction of large bone defects is of higher demand. To our knowledge, this is the first case of a successful clavicle reconstruction with a sufficient follow-up using a free vascularised fibula graft in a child. This case provides a technique description, considerations in the paediatric population, an overview of other techniques used, and a long-term follow-up.

Biochemical changes in barley plants after excessive supply of copper and manganese

The present study was undertaken to identify changes in some important proteins involved in CO2 fixation (Rubisco, Rubisco activase (RA), Rubisco binding protein (RBP)), NH4+ assimilation (glutamine synthetase (GS) and glutamate synthase (GOGAT)), using immunoblotting, and in the antioxidative defense as a result of Cu or Mn excess in barley leaves (Hordeum vulgare L. cv. Obzor). Activities and isoenzyme patterns of superoxide dismutase (SOD), ascorbate peroxidase (APX), guaiacol peroxidase (GPX) and catalase (CAT), as well as the levels of ascorbate (ASC), non-protein sulfhydryl groups, hydrogen peroxide and oxidative damage to proteins were determined. Data were correlated to the accumulation of Cu or Mn in the leaves after 5 days supply of heavy metal (HM) excess in the nutrient solution. In the highest Cu excess (1500 μM), Rubisco LS and SS were reduced considerably whereas under the highest Mn concentrations (18,300 μM) only minor changes in Rubisco subunits were detected. The RBP was diminished under the highest concentrations of both Cu or Mn. The bands of RA changed differently comparing Cu and Mn toxicity. GS decreased and GOGAT was absent under the highest concentration of Cu. At Mn excess Fd-GOGAT diminished whereas GS was not apparently changed. The development of toxicity symptoms corresponded to an accumulation of Cu or Mn in the leaves and to a gradual increase in protein carbonylation, a lower SOD activity and elevated CAT and GPX activities. APX activity was diminished under Mn toxicity and was not changed under Cu excess. Generally, changes in the isoenzyme profiles were similar under both toxicities. An accumulation of H2O2 was observed only at Mn excess. Contrasting changes in the low-molecular antioxidants were detected when comparing both toxicities. Cu excess affected mainly the non-protein SH groups, while Mn influenced the ASC content. Oxidative stress under Cu or Mn toxicity was most probably the consequence of depletion in low-molecular antioxidants as a result of their involvement in detoxification processes and disbalance in antioxidative enzymes. The link between heavy metal accumulation in leaves, leading to different display of oxidative stress, and changes in individual chloroplast proteins is discussed in the article.

The CODE MGEX orbit and clock solution

The Center for Orbit Determination in Europe (CODE) is contributing as a global Analysis center to the International GNSS Service (IGS) since many years. The processing of GPS and GLONASS data is well established in CODE’s ultra-rapid, rapid, and final product lines. With the introduction of new signals for the established and new GNSS, new challenges and opportunities are arising for the GNSS data management and processing. The IGS started the Multi-GNSS-EXperiment (MGEX) in 2012 in order to gain first experience with the new data formats and to develop new strategies for making optimal use of these additional measurements. CODE has started to contribute to IGS MGEX with a consistent, rigorously combined triple-system orbit solution (GPS, GLONASS, and Galileo). SLR residuals for the computed Galileo satellite orbits are of the order of 10 cm. Furthermore CODE established a GPS and Galileo clock solution. A quality assessment shows that these experimental orbit and clock products allow even a Galileo-only precise point positioning (PPP) with accuracies on the decimeter- (static PPP) to meter-level (kinematic PPP) for selected stations.

Influence of sample matrix on the alkaline extraction of Cr(VI) in soils and industrial materials

An accurate and efficient determination of the highly toxic Cr(VI) in solid materials is important to determine the total Cr(VI) inventory of contaminated sites and the Cr(VI) release potential from such sites into the environment. Most commonly, total Cr(VI) is extracted from solid materials following a hot alkaline extraction procedure (US EPA method 3060A) where a complete release of water-extractable and sparingly soluble Cr(VI) phase is achieved. This work presents an evaluation of matrix effects that may occur during the hot alkaline extraction and in the determination of the total Cr(VI) inventory of variably composed contaminated soils and industrial materials (cement, fly ash) and is compared to water-extractable Cr(VI) results. Method validation including multiple extractions and matrix spiking along with chemical and mineralogical characterization showed satisfying results for total Cr(VI) contents for most of the tested materials. However, unreliable results were obtained by applying method 3060A to anoxic soils due to the degradation of organic material and/or reactions with Fe2+-bearing mineral phases. In addition, in certain samples discrepant spike recoveries have to be also attributed to sample heterogeneity. Separation of possible extracted Cr(III) by applying cation-exchange cartridges prior to solution analysis further shows that under the hot alkaline extraction conditions only Cr(VI) is present in solution in measurable amounts, whereas Cr(III) gets precipitated as amorphous Cr(OH)3(am). It is concluded that prior to routine application of method 3060A to a new material type, spiking tests are recommended for the identification of matrix effects. In addition, the mass of extracted solid material should to be well adjusted to the heterogeneity of the Cr(VI) distribution in the material in question.

Biogenic and mineral composition and foraminiferal stratigraphy of sediment cores obtained in northern Germany

The Ratekau boring ended in clays of the so-called Asterigerina-Zone; these clays have shallow-water features in the uppermost samples. The clays are overlain by deep-water clays with pteropods; this formation is split into two parts by a shallow-water deposit. The fossiliferous series ends upward in sandy deposits with shallow-water fossils. The question is raised whether the two deep-water deposits might correspond to the Lower Doberg Beds (Eochattian) and the Upper Doberg Beds (Neochattian) at the Doberg hill, closer to the rim of the basin. All fossiliferous samples from this boring are thought to be of Late Oligocene age; the boundary towards the Middle Oligocene, however, could not be ascertained. The Vaale boring ended in rather typical Septaria clay of the Middle Oligocene. This clay is capped by some metres of unfossiliferous glauconite clays, which in turn are overlain by silts and silty clays with planktonic fossils identical to those found at Dingden locality. These deposits are tentatively dated as Early Miocene. The next higher series of samples consists of sands and clays deposited in shallower waters. They contain a rich fauna of benthic molluscs, which, according to the current notion in stratigraphy, would have a Reinbek Age. In addition, they contain a set of planktonic fossils which differs from the 'Lower Miocene' assemblages. These sands and clays are overlain by a thick series of marine sands very poor in fossils. Finally, four metres of clay with foraminifera, having Younger Miocene affinities, form the top of the fossiliferous sequence. The borings at Wulksfelde and Langenhorn were not far apart and their sediments are easily correlated. Both wells start below in continental 'Lignite Sands' and contain overlying shallow water sands and clays. These yielded Hemmoor benthic mollusca, supposed to indicate Lower Miocene in the relevant literature; however, we encountered their planktonic foraminifera in the uppermost Miocene as well. The same planktonic species were found in all samples of both borings. These deposits under discussion furthermore contain a particular pteropod species. They are overlain by a thick series of gypsiferous clays, with scarce fossils. The uppermost fossiliferous clays (probably Langenfelde Age) contain another pteropod species, not met with in other samples. The discrepancies between the plankton zonation and the traditional subdivision according to benthic molluscs in the borings of Vaale, Wulksfelde and Langenhorn (and in samples from Twistringen, Dingden and Antwerp localities as well) renders the time-stratigraphic value of the denominations Reinbek and Hemmoor rather doubtful. The samples of the Westerland boring can be placed in the Gram and Sylt stages of local chronostratigraphy on the strength of the Astarte series established by HINSCH. The Gram samples contain a typical pteropod species; both groups of samples contain the same planktonic foraminifera as the borings Wulksfelde and Langenhorn. Our material did not bring the problem of the Miocene-Pliocene boundary in this region any closer to a solution. In conclusion, it can be claimed that this investigation provides strong arguments that the usual recognition of Hemmoor and Reinbek does not correspond to well-defined chronostratigraphical units. A better chronostratigraphic subdivision has to be based on the examination of many more samples, and on a better understanding of the paleoecology of the fossils involved.

Surface Impedance Characterization for UTD Based Solution with IBC for Surface Fields on a Dielectric-Coated PEC Circular Cylinder

A novel formulation for the surface impedance characterization is introduced for the canonical problem of surface fields on a perfect electric conductor (PEC) circular cylinder with a dielectric coating due to a electric current source using the Uniform Theory of Diffraction (UTD) with an Impedance Boundary Condition (IBC). The approach is based on a TE/TM assumption of the surface fields from the original problem. Where this surface impedance fails, an optimization is performed to minimize the error in the SD Green?s function between the original problem and the equivalent one with the IBC. This new approach requires small changes in the available UTD based solution with IBC to include the geodesic ray angle and length dependence in the surface impedance formulas. This asymptotic method, accurate for large separations between source and observer points, in combination with spectral domain (SD) Green?s functions for multidielectric coatings leads to a new hybrid SD-UTD with IBC to calculate mutual coupling among microstrip patches on a multilayer dielectric-coated PEC circular cylinder. Results are compared with the eigenfunction solution in SD, where a very good agreement is met.

VISIONS Vehicular communication Improvement : solution based on IMS Operational Nodes and Services

Digital services and communications in vehicular scenarios provide the essential assets to improve road transport in several ways like reducing accidents, improving traffic efficiency and optimizing the transport of goods and people. Vehicular communications typically rely on VANET (Vehicular Ad hoc Networks). In these networks vehicles communicate with each other without the need of infrastructure. VANET are mainly oriented to disseminate information to the vehicles in certain geographic area for time critical services like safety warnings but present very challenging requirements that have not been successfully fulfilled nowadays. Some of these challenges are; channel saturation due to simultaneous radio access of many vehicles, routing protocols in topologies that vary rapidly, minimum quality of service assurance and security mechanisms to efficiently detect and neutralize malicious attacks. Vehicular services can be classified in four important groups: Safety, Efficiency, Sustainability and Infotainment. The benefits of these services for the transport sector are clear but many technological and business challenges need to be faced before a real mass market deployment. Service delivery platforms are not prepared for fulfilling the needs of this complex environment with restrictive requirements due to the criticism of some services To overcome this situation, we propose a solution called VISIONS “Vehicular communication Improvement: Solution based on IMS Operational Nodes and Services”. VISIONS leverages on IMS subsystem and NGN enablers, and follows the CALM reference Architecture standardized by ISO. It also avoids the use of Road Side Units (RSUs), reducing complexity and high costs in terms of deployment and maintenance. We demonstrate the benefits in the following areas: 1. VANET networks efficiency. VISIONS provide a mechanism for the vehicles to access valuable information from IMS and its capabilities through a cellular channel. This efficiency improvement will occur in two relevant areas: a. Routing mechanisms. These protocols are responsible of carrying information from a vehicle to another (or a group of vehicles) using multihop mechanisms. We do not propose a new algorithm but the use of VANET topology information provided through our solution to enrich the performance of these protocols. b. Security. Many aspects of security (privacy, key, authentication, access control, revocation mechanisms, etc) are not resolved in vehicular communications. Our solution efficiently disseminates revocation information to neutralize malicious nodes in the VANET. 2. Service delivery platform. It is based on extended enablers, reference architectures, standard protocols and open APIs. By following this approach, we reduce costs and resources for service development, deployment and maintenance. To quantify these benefits in VANET networks, we provide an analytical model of the system and simulate our solution in realistic scenarios. The simulations results demonstrate how VISIONS improves the performance of relevant routing protocols and is more efficient neutralizing security attacks than the widely proposed solutions based on RSUs. Finally, we design an innovative Social Network service based in our platform, explaining how VISIONS facilitate the deployment and usage of complex capabilities. RESUMEN Los servicios digitales y comunicaciones en entornos vehiculares proporcionan herramientas esenciales para mejorar el transporte por carretera; reduciendo el número de accidentes, mejorando la eficiencia del tráfico y optimizando el transporte de mercancías y personas. Las comunicaciones vehiculares generalmente están basadas en redes VANET (Vehicular Ad hoc Networks). En dichas redes, los vehículos se comunican entre sí sin necesidad de infraestructura. Las redes VANET están principalmente orientadas a difundir información (por ejemplo advertencias de seguridad) a los vehículos en determinadas zonas geográficas, pero presentan unos requisitos muy exigentes que no se han resuelto con éxito hasta la fecha. Algunos de estos retos son; saturación del canal de acceso de radio debido al acceso simultáneo de múltiples vehículos, la eficiencia de protocolos de encaminamiento en topologías que varían rápidamente, la calidad de servicio (QoS) y los mecanismos de seguridad para detectar y neutralizar los ataques maliciosos de manera eficiente. Los servicios vehiculares pueden clasificarse en cuatro grupos: Seguridad, Eficiencia del tráfico, Sostenibilidad, e Infotainment (información y entretenimiento). Los beneficios de estos servicios para el sector son claros, pero es necesario resolver muchos desafíos tecnológicos y de negocio antes de una implementación real. Las actuales plataformas de despliegue de servicios no están preparadas para satisfacer las necesidades de este complejo entorno con requisitos muy restrictivos debido a la criticidad de algunas aplicaciones. Con el objetivo de mejorar esta situación, proponemos una solución llamada VISIONS “Vehicular communication Improvement: Solution based on IMS Operational Nodes and Services”. VISIONS se basa en el subsistema IMS, las capacidades NGN y es compatible con la arquitectura de referencia CALM estandarizado por ISO para sistemas de transporte. También evita el uso de elementos en las carreteras, conocidos como Road Side Units (RSU), reduciendo la complejidad y los altos costes de despliegue y mantenimiento. A lo largo de la tesis, demostramos los beneficios en las siguientes áreas: 1. Eficiencia en redes VANET. VISIONS proporciona un mecanismo para que los vehículos accedan a información valiosa proporcionada por IMS y sus capacidades a través de un canal de celular. Dicho mecanismo contribuye a la mejora de dos áreas importantes: a. Mecanismos de encaminamiento. Estos protocolos son responsables de llevar información de un vehículo a otro (o a un grupo de vehículos) utilizando múltiples saltos. No proponemos un nuevo algoritmo de encaminamiento, sino el uso de información topológica de la red VANET a través de nuestra solución para enriquecer el funcionamiento de los protocolos más relevantes. b. Seguridad. Muchos aspectos de la seguridad (privacidad, gestión de claves, autenticación, control de acceso, mecanismos de revocación, etc) no están resueltos en las comunicaciones vehiculares. Nuestra solución difunde de manera eficiente la información de revocación para neutralizar los nodos maliciosos en la red. 2. Plataforma de despliegue de servicios. Está basada en capacidades NGN, arquitecturas de referencia, protocolos estándar y APIs abiertos. Siguiendo este enfoque, reducimos costes y optimizamos procesos para el desarrollo, despliegue y mantenimiento de servicios vehiculares. Para cuantificar estos beneficios en las redes VANET, ofrecemos un modelo de analítico del sistema y simulamos nuestra solución en escenarios realistas. Los resultados de las simulaciones muestran cómo VISIONS mejora el rendimiento de los protocolos de encaminamiento relevantes y neutraliza los ataques a la seguridad de forma más eficientes que las soluciones basadas en RSU. Por último, diseñamos un innovador servicio de red social basado en nuestra plataforma, explicando cómo VISIONS facilita el despliegue y el uso de las capacidades NGN.

Improved boundary elements in torsion problems

Since the epoch-making "memoir" of Saint-Venant in 1855 the torsion of prismatic and cilindrical bars has reduced to a mathematical problem: the calculation of an analytical function satisfying prescribed boundary values. For over one century, till the first applications of the F.E.M. to the problem, the only possibility of study in irregularly shaped domains was the beatiful, but limitated, theory of complex function analysis, several functional approaches and the finite difference method. Nevertheless in 1963 Jaswon published an interestingpaper which was nearly lost between the splendid F. E.M. boom. The method was extended by Rizzo to more complicated problems and definitively incorporated to the scientific community background through several lecture-notes of Cruse recently published, but widely circulated during past years. The work of several researches has shown the tremendous possibilities of the method which is today a recognized alternative to the well established F .E. procedure. In fact, the first comprehensive attempt to cover the method, has been recently published in textbook form. This paper is a contribution to the implementation of a difficulty which arises if the isoparametric elements concept is applicated to plane potential problems with sharp corners in the boundary domain. In previous works, these problems was avoided using two principal approximations: equating the fluxes round the corner or establishing a binode element (in fact, truncating the corner). The first approximation distortes heavily the solution in thecorner neighbourhood, and a great amount of element is neccesary to reduce its influence. The second is better suited but the price payed is increasing the size of the system of equations to be solved. In this paper an alternative formulation, consistent with the shape function chosen in the isoparametric representation, is presented. For ease of comprehension the formulation has been limited to the linear element. Nevertheless its extension to more refined elements is straight forward. Also a direct procedure for the assembling of the equations is presented in an attempt to reduce the in-core computer requirements.

Cognitive strategies for security in wireless sensor networks

Las redes de sensores inalámbricas son uno de los sectores con más crecimiento dentro de las redes inalámbricas. La rápida adopción de estas redes como solución para muchas nuevas aplicaciones ha llevado a un creciente tráfico en el espectro radioeléctrico. Debido a que las redes inalámbricas de sensores operan en las bandas libres Industrial, Scientific and Medical (ISM) se ha producido una saturación del espectro que en pocos años no permitirá un buen funcionamiento. Con el objetivo de solucionar este tipo de problemas ha aparecido el paradigma de Radio Cognitiva (CR). La introducción de las capacidades cognitivas en las redes inalámbricas de sensores permite utilizar estas redes para aplicaciones con unos requisitos más estrictos respecto a fiabilidad, cobertura o calidad de servicio. Estas redes que aúnan todas estas características son llamadas redes de sensores inalámbricas cognitivas (CWSNs). La mejora en prestaciones de las CWSNs permite su utilización en aplicaciones críticas donde antes no podían ser utilizadas como monitorización de estructuras, de servicios médicos, en entornos militares o de vigilancia. Sin embargo, estas aplicaciones también requieren de otras características que la radio cognitiva no nos ofrece directamente como, por ejemplo, la seguridad. La seguridad en CWSNs es un aspecto poco desarrollado al ser una característica no esencial para su funcionamiento, como pueden serlo el sensado del espectro o la colaboración. Sin embargo, su estudio y mejora es esencial de cara al crecimiento de las CWSNs. Por tanto, esta tesis tiene como objetivo implementar contramedidas usando las nuevas capacidades cognitivas, especialmente en la capa física, teniendo en cuenta las limitaciones con las que cuentan las WSNs. En el ciclo de trabajo de esta tesis se han desarrollado dos estrategias de seguridad contra ataques de especial importancia en redes cognitivas: el ataque de simulación de usuario primario (PUE) y el ataque contra la privacidad eavesdropping. Para mitigar el ataque PUE se ha desarrollado una contramedida basada en la detección de anomalías. Se han implementado dos algoritmos diferentes para detectar este ataque: el algoritmo de Cumulative Sum y el algoritmo de Data Clustering. Una vez comprobado su validez se han comparado entre sí y se han investigado los efectos que pueden afectar al funcionamiento de los mismos. Para combatir el ataque de eavesdropping se ha desarrollado una contramedida basada en la inyección de ruido artificial de manera que el atacante no distinga las señales con información del ruido sin verse afectada la comunicación que nos interesa. También se ha estudiado el impacto que tiene esta contramedida en los recursos de la red. Como resultado paralelo se ha desarrollado un marco de pruebas para CWSNs que consta de un simulador y de una red de nodos cognitivos reales. Estas herramientas han sido esenciales para la implementación y extracción de resultados de la tesis. ABSTRACT Wireless Sensor Networks (WSNs) are one of the fastest growing sectors in wireless networks. The fast introduction of these networks as a solution in many new applications has increased the traffic in the radio spectrum. Due to the operation of WSNs in the free industrial, scientific, and medical (ISM) bands, saturation has ocurred in these frequencies that will make the same operation methods impossible in the future. Cognitive radio (CR) has appeared as a solution for this problem. The networks that join all the mentioned features together are called cognitive wireless sensor networks (CWSNs). The adoption of cognitive features in WSNs allows the use of these networks in applications with higher reliability, coverage, or quality of service requirements. The improvement of the performance of CWSNs allows their use in critical applications where they could not be used before such as structural monitoring, medical care, military scenarios, or security monitoring systems. Nevertheless, these applications also need other features that cognitive radio does not add directly, such as security. The security in CWSNs has not yet been explored fully because it is not necessary field for the main performance of these networks. Instead, other fields like spectrum sensing or collaboration have been explored deeply. However, the study of security in CWSNs is essential for their growth. Therefore, the main objective of this thesis is to study the impact of some cognitive radio attacks in CWSNs and to implement countermeasures using new cognitive capabilities, especially in the physical layer and considering the limitations of WSNs. Inside the work cycle of this thesis, security strategies against two important kinds of attacks in cognitive networks have been developed. These attacks are the primary user emulator (PUE) attack and the eavesdropping attack. A countermeasure against the PUE attack based on anomaly detection has been developed. Two different algorithms have been implemented: the cumulative sum algorithm and the data clustering algorithm. After the verification of these solutions, they have been compared and the side effects that can disturb their performance have been analyzed. The developed approach against the eavesdropping attack is based on the generation of artificial noise to conceal information messages. The impact of this countermeasure on network resources has also been studied. As a parallel result, a new framework for CWSNs has been developed. This includes a simulator and a real network with cognitive nodes. This framework has been crucial for the implementation and extraction of the results presented in this thesis.

Contribution to the improvement of communication services in nanosatellite constellations using delay and disruption tolerant networking based architectures

Esta tesis se desarrolla dentro del marco de las comunicaciones satelitales en el innovador campo de los pequeños satélites también llamados nanosatélites o cubesats, llamados así por su forma cubica. Estos nanosatélites se caracterizan por su bajo costo debido a que usan componentes comerciales llamados COTS (commercial off-the-shelf) y su pequeño tamaño como los Cubesats 1U (10cm*10 cm*10 cm) con masa aproximada a 1 kg. Este trabajo de tesis tiene como base una iniciativa propuesta por el autor de la tesis para poner en órbita el primer satélite peruano en mi país llamado chasqui I, actualmente puesto en órbita desde la Estación Espacial Internacional. La experiencia de este trabajo de investigación me llevo a proponer una constelación de pequeños satélites llamada Waposat para dar servicio de monitoreo de sensores de calidad de agua a nivel global, escenario que es usado en esta tesis. Es ente entorno y dadas las características limitadas de los pequeños satélites, tanto en potencia como en velocidad de datos, es que propongo investigar una nueva arquitectura de comunicaciones que permita resolver en forma óptima la problemática planteada por los nanosatélites en órbita LEO debido a su carácter disruptivo en sus comunicaciones poniendo énfasis en las capas de enlace y aplicación. Esta tesis presenta y evalúa una nueva arquitectura de comunicaciones para proveer servicio a una red de sensores terrestres usando una solución basada en DTN (Delay/Disruption Tolerant Networking) para comunicaciones espaciales. Adicionalmente, propongo un nuevo protocolo de acceso múltiple que usa una extensión del protocolo ALOHA no ranurado, el cual toma en cuenta la prioridad del trafico del Gateway (ALOHAGP) con un mecanismo de contienda adaptativo. Utiliza la realimentación del satélite para implementar el control de la congestión y adapta dinámicamente el rendimiento efectivo del canal de una manera óptima. Asumimos un modelo de población de sensores finito y una condición de tráfico saturado en el que cada sensor tiene siempre tramas que transmitir. El desempeño de la red se evaluó en términos de rendimiento efectivo, retardo y la equidad del sistema. Además, se ha definido una capa de convergencia DTN (ALOHAGP-CL) como un subconjunto del estándar TCP-CL (Transmission Control Protocol-Convergency Layer). Esta tesis muestra que ALOHAGP/CL soporta adecuadamente el escenario DTN propuesto, sobre todo cuando se utiliza la fragmentación reactiva. Finalmente, esta tesis investiga una transferencia óptima de mensajes DTN (Bundles) utilizando estrategias de fragmentación proactivas para dar servicio a una red de sensores terrestres utilizando un enlace de comunicaciones satelitales que utiliza el mecanismo de acceso múltiple con prioridad en el tráfico de enlace descendente (ALOHAGP). El rendimiento efectivo ha sido optimizado mediante la adaptación de los parámetros del protocolo como una función del número actual de los sensores activos recibidos desde el satélite. También, actualmente no existe un método para advertir o negociar el tamaño máximo de un “bundle” que puede ser aceptado por un agente DTN “bundle” en las comunicaciones por satélite tanto para el almacenamiento y la entrega, por lo que los “bundles” que son demasiado grandes son eliminados o demasiado pequeños son ineficientes. He caracterizado este tipo de escenario obteniendo una distribución de probabilidad de la llegada de tramas al nanosatélite así como una distribución de probabilidad del tiempo de visibilidad del nanosatélite, los cuales proveen una fragmentación proactiva óptima de los DTN “bundles”. He encontrado que el rendimiento efectivo (goodput) de la fragmentación proactiva alcanza un valor ligeramente inferior al de la fragmentación reactiva. Esta contribución permite utilizar la fragmentación activa de forma óptima con todas sus ventajas tales como permitir implantar el modelo de seguridad de DTN y la simplicidad al implementarlo en equipos con muchas limitaciones de CPU y memoria. La implementación de estas contribuciones se han contemplado inicialmente como parte de la carga útil del nanosatélite QBito, que forma parte de la constelación de 50 nanosatélites que se está llevando a cabo dentro del proyecto QB50. ABSTRACT This thesis is developed within the framework of satellite communications in the innovative field of small satellites also known as nanosatellites (<10 kg) or CubeSats, so called from their cubic form. These nanosatellites are characterized by their low cost because they use commercial components called COTS (commercial off-the-shelf), and their small size and mass, such as 1U Cubesats (10cm * 10cm * 10cm) with approximately 1 kg mass. This thesis is based on a proposal made by the author of the thesis to put into orbit the first Peruvian satellite in his country called Chasqui I, which was successfully launched into orbit from the International Space Station in 2014. The experience of this research work led me to propose a constellation of small satellites named Waposat to provide water quality monitoring sensors worldwide, scenario that is used in this thesis. In this scenario and given the limited features of nanosatellites, both power and data rate, I propose to investigate a new communications architecture that allows solving in an optimal manner the problems of nanosatellites in orbit LEO due to the disruptive nature of their communications by putting emphasis on the link and application layers. This thesis presents and evaluates a new communications architecture to provide services to terrestrial sensor networks using a space Delay/Disruption Tolerant Networking (DTN) based solution. In addition, I propose a new multiple access mechanism protocol based on extended unslotted ALOHA that takes into account the priority of gateway traffic, which we call ALOHA multiple access with gateway priority (ALOHAGP) with an adaptive contention mechanism. It uses satellite feedback to implement the congestion control, and to dynamically adapt the channel effective throughput in an optimal way. We assume a finite sensor population model and a saturated traffic condition where every sensor always has frames to transmit. The performance was evaluated in terms of effective throughput, delay and system fairness. In addition, a DTN convergence layer (ALOHAGP-CL) has been defined as a subset of the standard TCP-CL (Transmission Control Protocol-Convergence Layer). This thesis reveals that ALOHAGP/CL adequately supports the proposed DTN scenario, mainly when reactive fragmentation is used. Finally, this thesis investigates an optimal DTN message (bundles) transfer using proactive fragmentation strategies to give service to a ground sensor network using a nanosatellite communications link which uses a multi-access mechanism with priority in downlink traffic (ALOHAGP). The effective throughput has been optimized by adapting the protocol parameters as a function of the current number of active sensors received from satellite. Also, there is currently no method for advertising or negotiating the maximum size of a bundle which can be accepted by a bundle agent in satellite communications for storage and delivery, so that bundles which are too large can be dropped or which are too small are inefficient. We have characterized this kind of scenario obtaining a probability distribution for frame arrivals to nanosatellite and visibility time distribution that provide an optimal proactive fragmentation of DTN bundles. We have found that the proactive effective throughput (goodput) reaches a value slightly lower than reactive fragmentation approach. This contribution allows to use the proactive fragmentation optimally with all its advantages such as the incorporation of the security model of DTN and simplicity in protocol implementation for computers with many CPU and memory limitations. The implementation of these contributions was initially contemplated as part of the payload of the nanosatellite QBito, which is part of the constellation of 50 nanosatellites envisaged under the QB50 project.