Estudios de especiación de arsénico y acumulación de metales en muestras de interés medioambiental : Arsenic speciation and metal accumulation studies in environmental samples

Se ha estudiado la determinación de especies de arsénico y de contenidos totales de arsénico y metales pesados, específicamente cadmio, cromo, cobre, níquel, plomo y cinc, en muestras de interés medioambiental por su elevada capacidad acumuladora de metales, concretamente algas marinas comestibles y plantas terrestres procedentes de suelos contaminados por la actividad minera. La determinación de contenidos totales se ha llevado a cabo mediante espectrometría de emisión atómica con plasma de acoplamiento inductivo (ICP‐AES), así como por espectrometría de fluorescencia atómica con generación de hidruros (HG‐AFS), para bajos contenidos de arsénico. Las muestras fueron mineralizadas en medio ácido y calentamiento en horno de microondas. Los métodos fueron validados a través de su aplicación a materiales de referencia de matriz similar a la de las muestras, certificados en contenidos totales de los elementos seleccionados. Los resultados obtenidos mostraron su elevada capacidad de bioabsorción, especialmente en relación a los elevados contenidos de arsénico encontrados en algunas especies de algas pardas (Phaeophytas). En las plantas, se calcularon los factores de translocación, acumulación y biodisponibilidad de los elementos estudiados, permitiendo identificar a la especie Corrigiola telephiifolia como posible acumuladora de plomo e hiperacumuladora de arsénico. La determinación de especies de arsénico hidrosolubles en las muestras objeto de estudio, se llevó a cabo por cromatografía líquida de alta eficacia (HPLC) acoplado a ICP‐AES, HG‐ICP‐AES y HG‐AFS, incluyendo una etapa previa de foto‐oxidación. Los métodos desarrollados, mediante intercambio aniónico y catiónico, permitieron la diferenciación de hasta once especies de arsénico. Para el análisis de las muestras, fue necesaria la optimización de métodos de extracción, seleccionándose la extracción asistida por microondas (MAE) con agua desionizada. Asimismo, se realizaron estudios de estabilidad de arsénico total y de las especies hidrosolubles presentes en las algas, tanto sobre la muestra sólida como en sus extractos acuosos, evaluando las condiciones de almacenamiento adecuadas. En el caso de las plantas, la aplicación del diseño factorial de experimentos permitió optimizar el método de extracción y diferenciar entre las especies de arsénico presentes en forma de iones sencillos de mayor movilidad y el arsénico más fuertemente enlazado a componentes estructurales. Los resultados obtenidos permitieron identificar la presencia de arseniato (As(V)) y arsenito (As(III)) en las plantas, así como de ácido monometilarsónico (MMA) y óxido de trimetilarsina (TMAO) en algunas especies. En la mayoría de las algas se encontraron especies tóxicas, tanto mayoritarias (arseniato) como minoritarias (ácido dimetilarsínico (DMA)), así como hasta cuatro arsenoazúcares. Los resultados obtenidos y su estudio a través de la legislación vigente, mostraron la necesidad de desarrollar una reglamentación específica para el control de este tipo de alimentos. La determinación de especies de arsénico liposolubles en las muestras de algas se llevó a cabo mediante HPLC, en modo fase inversa, acoplado a espectrometría de masas con plasma de acoplamiento inductivo (ICP‐MS) y con ionización por electrospray (ESI‐MS), permitiendo la elucidación estructural de estos compuestos a través de la determinación de sus masas moleculares. Para ello, fue necesaria la puesta a punto de métodos extracción y purificación de los extractos. La metodología desarrollada permitió identificar hasta catorce especies de arsénico liposolubles en las algas, tres de ellas correspondientes a hidrocarburos que contienen arsénico, y once a arsenofosfolípidos, además de dos especies desconocidas. Las masas moleculares de las especies identificadas fueron confirmadas mediante cromatografía de gases acoplada a espectrometría de masas (GC‐MS) y espectrometría de masas de alta resolución (HR‐MS). ABSTRACT The determination of arsenic species and total arsenic and heavy metal contents (cadmium, chromium, cooper, nickel, lead and zinc) in environmental samples, with high metal accumulator capacity, has been studied. The samples studied were edible marine algae and terrestrial plants from soils polluted by mining activities. The determination of total element contents was performed by inductively coupled plasma atomic emission spectrometry (ICP‐AES), as well as by hydride generation atomic fluorescence spectrometry (HG‐AFS) for low arsenic contents. The samples studied were digested in an acidic medium by heating in a microwave oven. The digestion methods were validated against reference materials, with matrix similar to sample matrix and certified in total contents of the elements studied. The results showed the high biosorption capacity of the samples studied, especially regarding the high arsenic contents in some species of brown algae (Phaeophyta division). In terrestrial plants, the translocation, accumulation and bioavailability factors of the elements studied were calculated. Thus, the plant species Corrigiola telephiifolia was identified as possible lead accumulator and arsenic hyperaccumulator. The determination of water‐soluble arsenic species in the samples studied was carried out by high performance liquid chromatography (HPLC) coupled to ICP‐AES, HG‐ICP‐AES and HG‐AFS, including a prior photo‐oxidation step. The chromatographic methods developed, by anion and cation exchange, allowed us to differentiate up to eleven arsenic species. The sample analysis required the optimization of extraction methods, choosing the microwave assisted extraction (MAE) with deionized water. On the other hand, the stability of total arsenic and water‐soluble arsenic species in algae, both in the solid samples and in the water extracts, was studied, assessing the suitable storage conditions. In the case of plant samples, the application of a multivariate experimental design allowed us to optimize the extraction method and differentiate between the arsenic species present as simple ions of higher mobility and the arsenic more strongly bound to structural components. The presence of arsenite (As(III)) and arsenate (As(V)) was identified in plant samples, as well as monomethylarsonic acid (MMA) and trimethylarsine oxide (TMAO) in some cases. Regarding algae, toxic arsenic species were found in most of them, both As(V) and dimethylarsinic acid (DMA), as well as up to four arsenosugars. These results were discussed according to the current legislation, showing the need to develop specific regulations to control this kind of food products. The determination of lipid‐soluble arsenic species in alga samples was performed by reversed‐phase HPLC coupled to inductively coupled plasma and electrospray mass spectrometry (ICP‐MS and ESI‐MS), in order to establish the structure of these compounds by determining the corresponding molecular masses. For this purpose, it was necessary to develop an extraction method, as well as a clean‐up method of the extracts. The method developed permitted the identification of fourteen lipid‐soluble arsenic compounds in algae, corresponding to three arsenic‐hydrocarbons and eleven arsenosugarphospholipids, as well as two unknown compounds. Accurate mass measurements of the identified compounds were performed by gas chromatography coupled to mass spectrometry (GC‐MS) and high resolution mass spectrometry (HR‐MS).

Intentions: a confident-based interaction design for smart spaces

The paradigm of ubiquitous computing has become a reference for the design of Smart Spaces. Current trends in Ambient Intelligence are increasingly related to the scope of Internet of Things. This paradigm has the potential to support cost-effective solutions in the fields of telecare, e-health and Ambient Assisted Living. Nevertheless, ubiquitous computing does not provide end users with a role for proactive interactions with the environment. Thus, the deployment of smart health care services at a private space like the home is still unsolved. This PhD dissertation aims to define a person-environment interaction model to foster acceptability and users confidence in private spaces by applying the concept of user-centred security and the human performance model of seven stages of action.

Topic selection in industry experiments

This paper shares our experience with initial negotiation and topic elicitation process for conducting industry experiments in six software development organizations in Finland. The process involved interaction with company representatives in the form of both multiple group discussions and separate face-to-face meetings. Fitness criteria developed by researchers were applied to the list of generated topics to decide on a common topic. The challenges we faced include diversity of proposed topics, communication gaps, skepticism about research methods, initial disconnect between research and industry needs, and lack of prior work relationship. Lessons learned include having enough time to establish trust with partners, importance of leveraging the benefits of training and skill development that are inherent in the experimental approach, uniquely positioning the experimental approach within the landscape of other validation approaches more familiar to industrial partners, and introducing the fitness criteria early in the process.

Electromagnetic Instability Studies in Fusion Plasmas Edge

Este trabajo esta dedicado al estudio de las estructuras macroscópicas conocidas en la literatura como filamentos o blobs que han sido observadas de manera universal en el borde de todo tipo de dispositivos de fusión por confinamiento magnético. Estos filamentos, celdas convectivas elongadas a lo largo de las líneas de campo que surgen en el plasma fuertemente turbulento que existe en este tipo de dispositivos, parecen dominar el transporte radial de partículas y energía en la región conocida como Scrape-off Layer, en la que las líneas de campo dejan de estar cerradas y el plasma es dirigido hacia la pared sólida que forma la cámara de vacío. Aunque el comportamiento y las leyes de escala de estas estructuras son relativamente bien conocidos, no existe aún una teoría generalmente aceptada acerca del mecanismo físico responsable de su formación, que constituye una de las principales incógnitas de la teoría de transporte del borde en plasmas de fusión y una cuestión de gran importancia práctica en el desarrollo de la siguiente generación de reactores de fusión (incluyendo dispositivos como ITER y DEMO), puesto que la eficiencia del confinamiento y la cantidad de energía depositadas en la pared dependen directamente de las características del transporte en el borde. El trabajo ha sido realizado desde una perspectiva eminentemente experimental, incluyendo la observación y el análisis de este tipo de estructuras en el stellarator tipo heliotrón LHD (un dispositivo de gran tamaño, capaz de generar plasmas de características cercanas a las necesarias en un reactor de fusión) y en el stellarator tipo heliac TJ-II (un dispositivo de medio tamaño, capaz de generar plasmas relativamente más fríos pero con una accesibilidad y disponibilidad de diagnósticos mayor). En particular, en LHD se observó la generación de filamentos durante las descargas realizadas en configuración de alta _ (alta presión cinética frente a magnética) mediante una cámara visible ultrarrápida, se caracterizó su comportamiento y se investigó, mediante el análisis estadístico y la comparación con modelos teóricos, el posible papel de la Criticalidad Autoorganizada en la formación de este tipo de estructuras. En TJ-II se diseñó y construyó una cabeza de sonda capaz de medir simultáneamente las fluctuaciones electrostáticas y electromagnéticas del plasma. Gracias a este nuevo diagnóstico se pudieron realizar experimentos con el fin de determinar la presencia de corriente paralela a través de los filamentos (un parámetro de gran importancia en su modelización) y relacionar los dos tipos de fluctuaciones por primera vez en un stellarator. Así mismo, también por primera vez en este tipo de dispositivo, fue posible realizar mediciones simultáneas de los tensores viscoso y magnético (Reynolds y Maxwell) de transporte de cantidad de movimiento. ABSTRACT This work has been devoted to the study of the macroscopic structures known in the literature as filaments or blobs, which have been observed universally in the edge of all kind of magnetic confinement fusion devices. These filaments, convective cells stretching along the magnetic field lines, arise from the highly turbulent plasma present in this kind of machines and seem to dominate radial transport of particles and energy in the region known as Scrapeoff Layer, in which field lines become open and plasma is directed towards the solid wall of the vacuum vessel. Although the behavior and scale laws of these structures are relatively well known, there is no generally accepted theory about the physical mechanism involved in their formation yet, which remains one of the main unsolved questions in the fusion plasmas edge transport theory and a matter of great practical importance for the development of the next generation of fusion reactors (including ITER and DEMO), since efficiency of confinement and the energy deposition levels on the wall are directly dependent of the characteristics of edge transport. This work has been realized mainly from an experimental perspective, including the observation and analysis of this kind of structures in the heliotron stellarator LHD (a large device capable of generating reactor-relevant plasma conditions) and in the heliac stellarator TJ-II (a medium-sized device, capable of relatively colder plasmas, but with greater ease of access and diagnostics availability). In particular, in LHD, the generation of filaments during high _ discharges (with high kinetic to magnetic pressure ratio) was observed by means of an ultrafast visible camera, and the behavior of this structures was characterized. Finally, the potential role of Self-Organized Criticality in the generation of filaments was investigated. In TJ-II, a probe head capable of measuring simultaneously electrostatic and electromagnetic fluctuations in the plasma was designed and built. Thanks to this new diagnostic, experiments were carried out in order to determine the presence of parallel current through filaments (one of the most important parameters in their modelization) and to related electromagnetic (EM) and electrostatic (ES) fluctuations for the first time in an stellarator. As well, also for the first time in this kind of device, measurements of the viscous and magnetic momentum transfer tensors (Reynolds and Maxwell) were performed.

Considerations on the success rate in aeronautical engineering studies in Spain

The relationship between different learning evaluation methods and the academic success in an aeronautical engineering degree in Spain is analysed. The study is based on data about the evolution of academic achievement obtained along the last ten year, along which the evaluation and learning’s methods have suffered huge changes.

Some methodological issues in the design of CIAO - A generic, parallel concurrent constraint system

We informally discuss several issues related to the parallel execution of logic programming systems and concurrent logic programming systems, and their generalization to constraint programming. We propose a new view of these systems, based on a particular definition of parallelism. We argüe that, under this view, a large number of the actual systems and models can be explained through the application, at different levéis of granularity, of only a few basic principies: determinism, non-failure, independence (also referred to as stability), granularity, etc. Also, and based on the convergence of concepts that this view brings, we sketch a model for the implementation of several parallel constraint logic programming source languages and models based on a common, generic abstract machine and an intermedíate kernel language.

Some methodological issues in the design of CIAO, a generic, parallel concurrent constraint system

We informally discuss several issues related to the parallel execution of logic programming systems and concurrent logic programming systems, and their generalization to constraint programming. We propose a new view of these systems, based on a particular definition of parallelism. We argüe that, under this view, a large number of the actual systems and models can be explained through the application, at different levéis of granularity, of only a few basic principies: determinism, non-failure, independence (also referred to as stability), granularity, etc. Also, and based on the convergence of concepts that this view brings, we sketch a model for the implementation of several parallel constraint logic programming source languages and models based on a common, generic abstract machine and an intermedíate kernel language.

Uncertainties in the design of support structures and foundations for offshore wind turbines

Offshore wind industry has exponentially grown in the last years. Despite this growth, there are still many uncertainties in this field. This paper analyzes some current uncertainties in the offshore wind market, with the aim of going one step further in the development of this sector. To do this, some already identified uncertainties compromising offshore wind farm structural design have been identified and described in the paper. Examples of these identified uncertainties are the design of the transition piece and the difficulties for the soil properties characterization. Furthermore, this paper deals with other uncertainties not identified yet due to the limited experience in the sector. To do that, current and most used offshore wind standards and recommendations related to the design of foundation and support structures (IEC 61400-1, 2005; IEC 61400-3, 2009; DNV-OS-J101, Design of Offshore Wind Turbine, 2013 and Rules and Guidelines Germanischer Lloyd, WindEnergie, 2005) have been analyzed. These new identified uncertainties are related to the lifetime and return period, loads combination, scour phenomenon and its protection, Morison e Froude Krilov and diffraction regimes, wave theory, different scale and liquefaction. In fact, there are a lot of improvements to make in this field. Some of them are mentioned in this paper, but the future experience in the matter will make it possible to detect more issues to be solved and improved.

Software industry experiments: a systematic literature review

There is no specialized survey of experiments conducted in the software industry. Goal: Identify the major features of software industry experiments, such as time distribution, independent and dependent variables, subject types, design types and challenges. Method: Systematic literature review, taking the form of a scoping study. Results: We have identified 10 experiments and five quasi-experiments up to July 2012. Most were run as of 2003. The main features of these studies are that they test technologies related to quality and management and analyse outcomes related to effectiveness and effort. Most experiments have a factorial design. The major challenges faced by experimenters are to minimize the cost of running the experiment for the company and to schedule the experiment so as not to interfere with production processes.

Participatory modelling to support decision making in water management under uncertainty: Two comparative case studies in the Guadiana river basin, Spain.

A participatory modelling process has been conducted in two areas of the Guadiana river (the upper and the middle sub-basins), in Spain, with the aim of providing support for decision making in the water management field. The area has a semi-arid climate where irrigated agriculture plays a key role in the economic development of the region and accounts for around 90% of water use. Following the guidelines of the European Water Framework Directive, we promote stakeholder involvement in water management with the aim to achieve an improved understanding of the water system and to encourage the exchange of knowledge and views between stakeholders in order to help building a shared vision of the system. At the same time, the resulting models, which integrate the different sectors and views, provide some insight of the impacts that different management options and possible future scenarios could have. The methodology is based on a Bayesian network combined with an economic model and, in the middle Guadiana sub-basin, with a crop model. The resulting integrated modelling framework is used to simulate possible water policy, market and climate scenarios to find out the impacts of those scenarios on farm income and on the environment. At the end of the modelling process, an evaluation questionnaire was filled by participants in both sub-basins. Results show that this type of processes are found very helpful by stakeholders to improve the system understanding, to understand each others views and to reduce conflict when it exists. In addition, they found the model an extremely useful tool to support management. The graphical interface, the quantitative output and the explicit representation of uncertainty helped stakeholders to better understand the implications of the scenario tested. Finally, the combination of different types of models was also found very useful, as it allowed exploring in detail specific aspects of the water management problems.

Blended learning in the design of collective protections in building works

The design of collective protections of construction works is a topic that is integrated within one of the MBTI subjects. This paper presents an experience for teaching the design of collective protection in building works. Teaching has been done in a bended way. This subject is taught as part of the content of a wider subject included in the Master "Building Technological Innovation" (MBTI) of the Universidad Politécnica de Madrid (UPM). This Master's degree is a postgraduate of research nature. Graduating in MBTI implies that students are in a position to begin their PhD thesis. At this stage, often students are not able to follow the rigour established by the schedule of classes. For this reason it is interesting that part of the teaching is developed in a non-classroom based way.

Advancements in the design and validation of an air pollution integrated assessment model for Spain

This paper describes the design and application of the Atmospheric Evaluation and Research Integrated model for Spain (AERIS). Currently, AERIS can provide concentration profiles of NO2, O3, SO2, NH3, PM, as a response to emission variations of relevant sectors in Spain. Results are calculated using transfer matrices based on an air quality modelling system (AQMS) composed by the WRF (meteorology), SMOKE (emissions) and CMAQ (atmospheric-chemical processes) models. The AERIS outputs were statistically tested against the conventional AQMS and observations, revealing a good agreement in both cases. At the moment, integrated assessment in AERIS focuses only on the link between emissions and concentrations. The quantification of deposition, impacts (health, ecosystems) and costs will be introduced in the future. In conclusion, the main asset of AERIS is its accuracy in predicting air quality outcomes for different scenarios through a simple yet robust modelling framework, avoiding complex programming and long computing times.

El "Anclaje y Ajuste", una herramienta de Marketing para analizar el poder de las referencias en el Arte, el Diseño y la Arquitectura = "Anchoring and Adjustment", a Marketing tool to analyse references in Art, Design and Architecture

El "Anclaje y Ajuste", una herramienta de Marketing para analizar el poder de las referencias en el Arte, el Diseño y la Arquitectura = "Anchoring and Adjustment", a Marketing tool to analyse references in Art, Design and Architecture