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).

Self-organized colloidal quantum dots and metal nanoparticles for plasmon-enhanced intermediate-band solar cells

A colloidal deposition technique is presented to construct long-range ordered hybrid arrays of self-assembled quantum dots and metal nanoparticles. Quantum dots are promising for novel opto-electronic devices but, in most cases, their optical transitions of interest lack sufficient light absorption to provide a significant impact in their implementation. A potential solution is to couple the dots with localized plasmons in metal nanoparticles. The extreme confinement of light in the near-field produced by the nanoparticles can potentially boost the absorption in the quantum dots by up to two orders of magnitude. In this work, light extinction measurements are employed to probe the plasmon resonance of spherical gold nanoparticles in lead sulfide colloidal quantum dots and amorphous silicon thin-films. Mie theory computations are used to analyze the experimental results and determine the absorption enhancement that can be generated by the highly intense near-field produced in the vicinity of the gold nanoparticles at their surface plasmon resonance. The results presented here are of interest for the development of plasmon-enhanced colloidal nanostructured photovoltaic materials, such as colloidal quantum dot intermediate-band solar cells.

Configuration management and product lines to enhance the replication process in software engineering

This research is concerned with the experimental software engineering area, specifically experiment replication. Replication has traditionally been viewed as a complex task in software engineering. This is possibly due to the present immaturity of the experimental paradigm applied to software development. Researchers usually use replication packages to replicate an experiment. However, replication packages are not the solution to all the information management problems that crop up when successive replications of an experiment accumulate. This research borrows ideas from the software configuration management and software product line paradigms to support the replication process. We believe that configuration management can help to manage and administer information from one replication to another: hypotheses, designs, data analysis, etc. The software product line paradigm can help to organize and manage any changes introduced into the experiment by each replication. We expect the union of the two paradigms in replication to improve the planning, design and execution of further replications and their alignment with existing replications. Additionally, this research work will contribute a web support environment for archiving information related to different experiment replications. Additionally, it will provide flexible enough information management support for running replications with different numbers and types of changes. Finally, it will afford massive storage of data from different replications. Experimenters working collaboratively on the same experiment must all have access to the different experiments.

Facing the climate change challenges in the mining and mineral industry as providers of a sustainable manufacturing process

A sustainable manufacturing process must rely on an also sustainable raw materials and energy supply. This paper is intended to show the results of the studies developed on sustainable business models for the minerals industry as a fundamental previous part of a sustainable manufacturing process. As it has happened in other economic activities, the mining and minerals industry has come under tremendous pressure to improve its social, developmental, and environmental performance. Mining, refining, and the use and disposal of minerals have in some instances led to significant local environmental and social damage. Nowadays, like in other parts of the corporate world, companies are more routinely expected to perform to ever higher standards of behavior, going well beyond achieving the best rate of return for shareholders. They are also increasingly being asked to be more transparent and subject to third-party audit or review, especially in environmental aspects. In terms of environment, there are three inter-related areas where innovation and new business models can make the biggest difference: carbon, water and biodiversity. The focus in these three areas is for two reasons. First, the industrial and energetic minerals industry has significant footprints in each of these areas. Second, these three areas are where the potential environmental impacts go beyond local stakeholders and communities, and can even have global impacts, like in the case of carbon. So prioritizing efforts in these areas will ultimately be a strategic differentiator as the industry businesses continues to grow. Over the next forty years, world?s population is predicted to rise from 6.300 million to 9.500 million people. This will mean a huge demand of natural resources. Indeed, consumption rates are such that current demand for raw materials will probably soon exceed the planet?s capacity. As awareness of the actual situation grows, the public is demanding goods and services that are even more environmentally sustainable. This means that massive efforts are required to reduce the amount of materials we use, including freshwater, minerals and oil, biodiversity, and marine resources. It?s clear that business as usual is no longer possible. Today, companies face not only the economic fallout of the financial crisis; they face the substantial challenge of transitioning to a low-carbon economy that is constrained by dwindling natural resources easily accessible. Innovative business models offer pioneering companies an early start toward the future. They can signal to consumers how to make sustainable choices and provide reward for both the consumer and the shareholder. Climate change and carbon remain major risk discontinuities that we need to better understand and deal with. In the absence of a global carbon solution, the principal objective of any individual country should be to reduce its global carbon emissions by encouraging conservation. The mineral industry internal response is to continue to focus on reducing the energy intensity of our existing operations through energy efficiency and the progressive introduction of new technology. Planning of the new projects must ensure that their energy footprint is minimal from the start. These actions will increase the long term resilience of the business to uncertain energy and carbon markets. This focus, combined with a strong demand for skills in this strategic area for the future requires an appropriate change in initial and continuing training of engineers and technicians and their awareness of the issue of eco-design. It will also need the development of measurement tools for consistent comparisons between companies and the assessments integration of the carbon footprint of mining equipments and services in a comprehensive impact study on the sustainable development of the Economy.

Molecular physiology of nickel and cobalt homeostasis in Rhizobium leguminosarum.

Transition metals such as Fe, Cu, Mn, Ni, or Co are essential nutrients, as they are constitutive elements of a significant fraction of cell proteins. Such metals are present in the active site of many enzymes, and also participate as structural elements in different proteins. From a chemical point of view, metals have a defined order of affinity for binding, designated as the Irving-Williams series (Irving and Williams, 1948) Mg2+ menor que Mn2+ menor que Fe2+ menor que Co2+ menor que Ni2+ menor que Cu2+mayor queZn2+ Since cells contain a high number of different proteins harbouring different metal ions, a simplistic model in which proteins are synthesized and metals imported into a ?cytoplasmic soup? cannot explain the final product that we find in the cell. Instead we need to envisage a complex model in which specific ligands are present in definite amounts to leave the right amounts of available metals and protein binding sites, so specific pairs can bind appropriately. A critical control on the amount of ligands and metal present is exerted through specific metal-responsive regulators able to induce the synthesis of the right amount of ligands (essentially metal binding proteins), import and efflux proteins. These systems are adapted to establish the metal-protein equilibria compatible with the formation of the right metalloprotein complexes. Understanding this complex network of interactions is central to the understanding of metal metabolism for the synthesis of metalloenzymes, a key topic in the Rhizobium-legume symbiosis. In the case of the Rhizobium leguminosarum bv viciae (Rlv) UPM791 -Pisum sativum symbiotic system, the concentration of nickel in the plant nutrient solution is a limiting factor for hydrogenase expression, and provision of high amounts of this element to the plant nutrient solution is required to ensure optimal levels of enzyme synthesis (Brito et al., 1994).

Utilizing the Internet of Things to promote energy awareness and efficiency at discrete production processes: Practices and methodology

El actual contexto de fabricación, con incrementos en los precios de la energía, una creciente preocupación medioambiental y cambios continuos en los comportamientos de los consumidores, fomenta que los responsables prioricen la fabricación respetuosa con el medioambiente. El paradigma del Internet de las Cosas (IoT) promete incrementar la visibilidad y la atención prestada al consumo de energía gracias tanto a sensores como a medidores inteligentes en los niveles de máquina y de línea de producción. En consecuencia es posible y sencillo obtener datos de consumo de energía en tiempo real proveniente de los procesos de fabricación, pero además es posible analizarlos para incrementar su importancia en la toma de decisiones. Esta tesis pretende investigar cómo utilizar la adopción del Internet de las Cosas en el nivel de planta de producción, en procesos discretos, para incrementar la capacidad de uso de la información proveniente tanto de la energía como de la eficiencia energética. Para alcanzar este objetivo general, la investigación se ha dividido en cuatro sub-objetivos y la misma se ha desarrollado a lo largo de cuatro fases principales (en adelante estudios). El primer estudio de esta tesis, que se apoya sobre una revisión bibliográfica comprehensiva y sobre las aportaciones de expertos, define prácticas de gestión de la producción que son energéticamente eficientes y que se apoyan de un modo preeminente en la tecnología IoT. Este primer estudio también detalla los beneficios esperables al adoptar estas prácticas de gestión. Además, propugna un marco de referencia para permitir la integración de los datos que sobre el consumo energético se obtienen en el marco de las plataformas y sistemas de información de la compañía. Esto se lleva a cabo con el objetivo último de remarcar cómo estos datos pueden ser utilizados para apalancar decisiones en los niveles de procesos tanto tácticos como operativos. Segundo, considerando los precios de la energía como variables en el mercado intradiario y la disponibilidad de información detallada sobre el estado de las máquinas desde el punto de vista de consumo energético, el segundo estudio propone un modelo matemático para minimizar los costes del consumo de energía para la programación de asignaciones de una única máquina que deba atender a varios procesos de producción. Este modelo permite la toma de decisiones en el nivel de máquina para determinar los instantes de lanzamiento de cada trabajo de producción, los tiempos muertos, cuándo la máquina debe ser puesta en un estado de apagada, el momento adecuado para rearrancar, y para pararse, etc. Así, este modelo habilita al responsable de producción de implementar el esquema de producción menos costoso para cada turno de producción. En el tercer estudio esta investigación proporciona una metodología para ayudar a los responsables a implementar IoT en el nivel de los sistemas productivos. Se incluye un análisis del estado en que se encuentran los sistemas de gestión de energía y de producción en la factoría, así como también se proporcionan recomendaciones sobre procedimientos para implementar IoT para capturar y analizar los datos de consumo. Esta metodología ha sido validada en un estudio piloto, donde algunos indicadores clave de rendimiento (KPIs) han sido empleados para determinar la eficiencia energética. En el cuarto estudio el objetivo es introducir una vía para obtener visibilidad y relevancia a diferentes niveles de la energía consumida en los procesos de producción. El método propuesto permite que las factorías con procesos de producción discretos puedan determinar la energía consumida, el CO2 emitido o el coste de la energía consumida ya sea en cualquiera de los niveles: operación, producto o la orden de fabricación completa, siempre considerando las diferentes fuentes de energía y las fluctuaciones en los precios de la misma. Los resultados muestran que decisiones y prácticas de gestión para conseguir sistemas de producción energéticamente eficientes son posibles en virtud del Internet de las Cosas. También, con los resultados de esta tesis los responsables de la gestión energética en las compañías pueden plantearse una aproximación a la utilización del IoT desde un punto de vista de la obtención de beneficios, abordando aquellas prácticas de gestión energética que se encuentran más próximas al nivel de madurez de la factoría, a sus objetivos, al tipo de producción que desarrolla, etc. Así mismo esta tesis muestra que es posible obtener reducciones significativas de coste simplemente evitando los períodos de pico diario en el precio de la misma. Además la tesis permite identificar cómo el nivel de monitorización del consumo energético (es decir al nivel de máquina), el intervalo temporal, y el nivel del análisis de los datos son factores determinantes a la hora de localizar oportunidades para mejorar la eficiencia energética. Adicionalmente, la integración de datos de consumo energético en tiempo real con datos de producción (cuando existen altos niveles de estandarización en los procesos productivos y sus datos) es esencial para permitir que las factorías detallen la energía efectivamente consumida, su coste y CO2 emitido durante la producción de un producto o componente. Esto permite obtener una valiosa información a los gestores en el nivel decisor de la factoría así como a los consumidores y reguladores. ABSTRACT In today‘s manufacturing scenario, rising energy prices, increasing ecological awareness, and changing consumer behaviors are driving decision makers to prioritize green manufacturing. The Internet of Things (IoT) paradigm promises to increase the visibility and awareness of energy consumption, thanks to smart sensors and smart meters at the machine and production line level. Consequently, real-time energy consumption data from the manufacturing processes can be easily collected and then analyzed, to improve energy-aware decision-making. This thesis aims to investigate how to utilize the adoption of the Internet of Things at shop floor level to increase energy–awareness and the energy efficiency of discrete production processes. In order to achieve the main research goal, the research is divided into four sub-objectives, and is accomplished during four main phases (i.e., studies). In the first study, by relying on a comprehensive literature review and on experts‘ insights, the thesis defines energy-efficient production management practices that are enhanced and enabled by IoT technology. The first study also explains the benefits that can be obtained by adopting such management practices. Furthermore, it presents a framework to support the integration of gathered energy data into a company‘s information technology tools and platforms, which is done with the ultimate goal of highlighting how operational and tactical decision-making processes could leverage such data in order to improve energy efficiency. Considering the variable energy prices in one day, along with the availability of detailed machine status energy data, the second study proposes a mathematical model to minimize energy consumption costs for single machine production scheduling during production processes. This model works by making decisions at the machine level to determine the launch times for job processing, idle time, when the machine must be shut down, ―turning on‖ time, and ―turning off‖ time. This model enables the operations manager to implement the least expensive production schedule during a production shift. In the third study, the research provides a methodology to help managers implement the IoT at the production system level; it includes an analysis of current energy management and production systems at the factory, and recommends procedures for implementing the IoT to collect and analyze energy data. The methodology has been validated by a pilot study, where energy KPIs have been used to evaluate energy efficiency. In the fourth study, the goal is to introduce a way to achieve multi-level awareness of the energy consumed during production processes. The proposed method enables discrete factories to specify energy consumption, CO2 emissions, and the cost of the energy consumed at operation, production and order levels, while considering energy sources and fluctuations in energy prices. The results show that energy-efficient production management practices and decisions can be enhanced and enabled by the IoT. With the outcomes of the thesis, energy managers can approach the IoT adoption in a benefit-driven way, by addressing energy management practices that are close to the maturity level of the factory, target, production type, etc. The thesis also shows that significant reductions in energy costs can be achieved by avoiding high-energy price periods in a day. Furthermore, the thesis determines the level of monitoring energy consumption (i.e., machine level), the interval time, and the level of energy data analysis, which are all important factors involved in finding opportunities to improve energy efficiency. Eventually, integrating real-time energy data with production data (when there are high levels of production process standardization data) is essential to enable factories to specify the amount and cost of energy consumed, as well as the CO2 emitted while producing a product, providing valuable information to decision makers at the factory level as well as to consumers and regulators.

Growth response of broilers to lysine levels and hydrolyzed porcine digestive mucosa (Palbio) inclusion in diet from 1 to 21 d of age

Palbio (PAL, Palbio 50 RD, Bioibérica, Spain) is a protein concentrate based on hydrolyzed porcine digestive mucosa dried under a fluid bed system over a soybean carrier, currently used in piglet feeds. The digestibility of PAL is very high and the product may be an excellent source of protein for young chicks. An experiment was conducted with 1,280 straight-run one-d-old Ross 308 chicks to evaluate the growth response of broilers to dietary inclusion of PAL.

Towards description and optimization of abstract machines in an extension of prolog

Competitive abstract machines for Prolog are usually large, intricate, and incorpórate sophisticated optimizations. This makes them difñcult to code, optimize, and, especially, maintain and extend. This is partly due to the fact that efñciency considerations make it necessary to use low-level languages in their implementation. Writing the abstract machine (and ancillary code) in a higher-level language can help harness this inherent complexity. In this paper we show how the semantics of basic components of an efficient virtual machine for Prolog can be described using (a variant of) Prolog which retains much of its semantics. These descriptions are then compiled to C and assembled to build a complete bytecode emulator. Thanks to the high level of the language used and its closeness to Prolog the abstract machine descriptions can be manipulated using standard Prolog compilation and optimization techniques with relative ease. We also show how, by applying program transformations selectively, we obtain abstract machine implementations whose performance can match and even exceed that of highly-tuned, hand-crafted emulators.

Balancing software engineering education and industrial needs

In the world of information and communications technologies the demand for professionals with software engineering skills grows at an exponential rate. On this ground, we have conducted a study to help both academia and the software industry form a picture of the relationship between the competences of recent graduates of undergraduate and graduate software engineering programmes and the tasks that these professionals are to perform as part of their jobs in industry. Thanks to this study, academia will be able to observe which skills demanded by industry the software engineering curricula do or do not cater for, and industry will be able to ascertain which tasks a recent software engineering programme graduate is well qualified to perform. The study focuses on the software engineering knowledge guidelines provided in SE2004 and GSwE2009, and the job profiles identified by Career Space.

Control of a solar dryer through using a fuzzy logic and low-cost model-based sensor

Solar drying is one of the important processes used for extending the shelf life of agricultural products. Regarding consumer requirements, solar drying should be more suitable in terms of curtailing total drying time and preserving product quality. Therefore, the objective of this study was to develop a fuzzy logic-based control system, which performs a ?human-operator-like? control approach through using the previously developed low-cost model-based sensors. Fuzzy logic toolbox of MatLab and Borland C++ Builder tool were utilized to develop a required control system. An experimental solar dryer, constructed by CONA SOLAR (Austria) was used during the development of the control system. Sensirion sensors were used to characterize the drying air at different positions in the dryer, and also the smart sensor SMART-1 was applied to be able to include the rate of wood water extraction into the control system (the difference of absolute humidity of the air between the outlet and the inlet of solar dryer is considered by SMART-1 to be the extracted water). A comprehensive test over a 3 week period for different fuzzy control models has been performed, and data, obtained from these experiments, were analyzed. Findings from this study would suggest that the developed fuzzy logic-based control system is able to tackle difficulties, related to the control of solar dryer process.

Problemática estructural y de funcionamiento de la cadena de valor del jamón ibérico de bellota: el caso de Guijuelo en España

El sector porcino ibérico es un sector típicamente español. La imagen que asocia el consumidor a los productos ibéricos es la correspondiente a los productos elaborados a partir de cerdos ibéricos en explotaciones extensivas, (dehesas), y cebados en montanera. Sin embargo, según los datos publicados por el Ministerio de Agricultura, Alimentación y Medio Ambiente, más de un 70 por ciento de los cerdos ibéricos que se producen en España son criados en granjas intensivas. El sector porcino ibérico está en pleno proceso de cambio, tanto por las variaciones que se derivan de la crisis que sufre el sector, como por las modificaciones que se esperan en la norma de calidad, recientemente acordadas. En este entorno en el que existe una reducción importante de los márgenes comerciales en todos los eslabones de la cadena de valor del jamón ibérico de bellota, adquiere importancia el estudio de su estructura y funcionamiento, la determinación de los aspectos que mejoran la eficiencia económica a lo largo de la misma y su concordancia a lo largo de ella. Así mismo, un sector de los consumidores comienza a buscar productos de calidad, se interesa por productos con determinados etiquetados que garantizan la calidad o unas determinadas prácticas de producción y elaboración, como sucede con los productos ecológicos. Existen numerosos estudios sobre distintos aspectos del sector porcino ibérico, realizados por distintas instituciones, como universidades, instituciones privadas y proyectos europeos. En general, se centran en la mejora de la producción de los cerdos ibéricos o en la mejora de la elaboración de los jamones. La novedad de la investigación realizada en la presente Tesis Doctoral reside en el estudio de los aspectos que determinan la mayor eficiencia económica de la cadena de valor del jamón ibérico de bellota de la denominación de origen de Guijuelo, y en las características que aporta al jamón ibérico de bellota la producción ecológica frente a la convencional. Resumen Los objetivos planteados en esta investigación son la mejora de la cadena de valor del jamón ibérico de bellota de la denominación de origen de Guijuelo, mediante el estudio de la problemática estructural y de funcionamiento de la misma. Como objetivos específicos se proponen la mejora de la eficiencia económica en las relaciones comerciales entre los distintos eslabones de la cadena de valor, y el impulso de la oferta de los productos ecológicos de ibérico, mediante el estudio comparativo de las producciones convencionales y ecológicas. Para alcanzar estos objetivos la metodología utilizada es la cadena de valor agroalimentaria, utilizando como herramientas de análisis el método Delphi y la realización de un análisis DAFO del sector porcino ibérico. Las fuentes de información primarias utilizadas proceden por una parte de la colaboración realizada en el proyecto europeo Q-Porkchains, coordinado por el Dr. Jacques H. Trienekens, y por otra parte de los cuestionarios especialmente diseñados para el análisis Delphi realizado. Las fuentes de información secundarias proceden de artículos académicos publicados, de artículos de revistas especializadas en el sector y de informes y estadísticas publicados por el Ministerio de Agricultura, Alimentación y Medio Ambiente. Las conclusiones de la investigación son las siguientes. Las relaciones comerciales de la cadena de valor estudiada están gestionadas, ya que se otorga gran valor a las relaciones comerciales basadas en la confianza, tanto en el aprovisionamiento de productos como en la venta de los mismos en cada eslabón. Sin embargo, no se gestiona adecuadamente la gama de productos que se oferta a lo largo de la cadena de valor, puesto que los eslabones de la misma obtienen diferente eficiencia económica para el mismo producto. Por otra parte, aunque la denominación de origen de Guijuelo es una marca conocida por el consumidor, el esfuerzo por tener una marca colectiva de calidad no ha sido totalmente satisfactorio, en especial para el eslabón de la distribución. Por esta razón, es importante resaltar que es recomendable la creación de una marca propia que cuide la calidad con especial atención, modificando incluso las empresas integrantes de la cadena de valor si el objetivo de calidad no coincide. Es importante garantizar la calidad del producto al consumidor, mediante la trasmisión la información generada por los informes de inspección y certificación realizados por las entidades correspondientes en relación a la norma de calidad de los productos de cerdo ibérico y por el Consejo Regulador de Guijuelo. Se requiere un estudio detallado de los posibles nichos de mercado para llegar a los clientes que buscan un producto de calidad diferenciada como es el jamón ibérico de denominación de origen de Guijuelo. Dentro de los posibles clientes debe tenerse en consideración al colectivo de personas alérgicas, ya que no se encuentran con facilidad en el mercado productos cárnicos de cerdo libres de alérgenos. Por último, la innovación es muy importante en este sector, y pueden ofertarse nuevos productos que ayuden al acortamiento de la cadena de valor, como podría ser la carne fresca de cerdo ibérico de bellota. La producción ecológica de porcino ibérico, en la actualidad no es significativa. El manejo que se realiza de los cerdos ibéricos convencionales de bellota es muy similar al manejo que se realiza de los cerdos ecológicos, salvo en la alimentación que reciben los cerdos ibéricos antes del cebo en montanera y en los medicamentos permitidos en ambas producciones. La producción de porcino ecológico de bellota puede ser interesante para la exportación. Los jamones ibéricos de bellota dispondrían de un sello que garantiza un manejo tradicional –como se realiza en muchas explotaciones extensivas de cerdos ibéricos de bellota-, y que es apreciado por los consumidores de otros países, dispuestos a pagar por productos de calidad diferenciada. Este tipo de producción quizá podría solventar la limitación al ámbito nacional de la norma de calidad de los productos de cerdo ibérico. La falta de claridad y unanimidad en el sector sobre la calidad de los productos de ibéricos que se percibe en los cambios previstos en la legislación, y el interés del eslabón de la industria elaboradora de jamones en calidades no ligadas a producciones extensivas sino intensivas, por su mayor volumen de ventas y sus mejores rendimientos, mueven a los productores de “ibérico puro de bellota” a desmarcarse del sector “ibérico”, donde el peso del producto ibérico cruzado de pienso tiene mucho peso en las decisiones que se toman. The Iberian pork industry is a typically Spanish industry. The associated image by the consumer to these products corresponds to products made from Iberian pigs in extensive farms (meadows), and fattened in open range. However, according to data released by the Ministry of Agriculture, Food and Environment, more than 70 percent of the Iberian pigs produced in Spain are raised on factory farms. The Iberian pork industry is in process of change, both by modifications resulting from the crisis in the sector, and the expected ones in the quality standard, recently agreed. In this environment where there is a significant reduction in trade margins in all links of the value chain of Iberian ham, becomes important to study its structure and operation, identifying the aspects that improve economic efficiency along the value chain and their concordance along it. Likewise, part of the consumers begins searching for quality products, they are interested in certain products that guarantee some sort of quality or production and processing practices, like organic products. There are several studies on various aspects of the Iberian pork industry, made by different institutions, such as universities, private institutions and some European projects. In general, their goal is focused on improving the Iberian hog production or on improving the elaboration of hams. The novelty of the research conducted in this PhD thesis lies in the study of the aspects that determine the economic efficiency of the value chain of Iberian ham from Guijuelo designation of origin, and the comparison between the features that organic or conventional production of Iberian ham brings to it. The objectives propound in this research are the improvement of the value chain of Iberian ham from Guijuelo designation of origin, through the study of its structural and operational problematic. The proposed specific objectives are the improvement of the economic efficiency Resumen in trade relations between the different links in the value chain, and the promotion of the supply of Iberian organic pork products, through the comparative study of conventional and organic productions. In order to achieve these objectives, the used methodology is the agrifood value chain, using as analysis tools the Delphi method, and a SWOT analysis of the Iberian pork industry. The primary sources of information come partly from the collaboration in the European project Q-Porkchains, coordinated by Dr. Jacques Trienekens, and partly from the questionnaires specially designed for the Delphi analysis performed. The secondary sources come from published academic papers, specialized journal articles and reports published by the Ministry of Agriculture, Food and Environment. The research conclusions are as follows. Trade relations in the studied value chain are managed, as it is granted a great value to business relationships based on trust, both in the supply of products and in the sale in each link. However, the portfolio that is offered throughout the value chain is not properly managed, since the economic efficiency obtained for the same product is different in each link. Moreover, although the designation of origin of Guijuelo is a well-known brand, the effort made to acquire a collective quality trademark has not been entirely satisfactory, especially in the distribution link. Due to it, it is important to highlight that it is recommended to create a brand focused on quality, and indeed to change the firms integrating the vale chain, if the goal is not shared by all the companies. It is essential to ensure the quality of the product to the consumer, through the transmission of the available information related to the quality standard of Iberian pork products and of the Guijuelo Regulating Council. A detailed study of potential niche markets is required, in order to reach customers looking for a differentiated quality product as Iberian ham of Guijuelo designation of origin. It should be taken into consideration the group of allergy sufferers as potential customers, as they do not easily find pork products in the market free of allergens. Innovation is very important in this industry, and new products could be commercialized that help to shorten the value chain, as fresh acorn Iberian pork. Nowadays, the organic production of Iberian pork products is not significant. The operation is very similar in both conventional and organic production of Iberian pork products, except in the food received by Iberian hogs and the sort of medicinal treatments allowed in each production. The organic acorn Iberian pork production could be interesting for export. Acorn Iberian hams would have a well-known hallmark, which guarantees a traditional production, -as it is done in many extensive holdings of Iberian acorn-pigs-, and that is appreciated by consumers in other countries This niche of consumers could pay for differentiated quality products. Perhaps, this sort of production could solve the limitation to national scope of the quality standard of Iberian pork products. The lack of clarity and unanimity in the industry on the quality of Iberian pork products has been perceived in the agreed changes of the legislation as well as the interest of the processing industry in hams of quality categories which are not linked to extensive but intensive productions, due to their higher sales volume and better yields. This situation pushed "acorn pure Iberian " pigs farmers to split from the Iberian industry, where the importance of cross Iberian pig from intensive farms is growing so high that they can influence the negotiations and decisions taken inside and outside the industry.

Protein isolate and inulin: chemical, rheological and structural basis

Soy protein isolate is typical vegetable protein with health-enhancing activities. Inulin, a prebiotic no digestible carbohydrate, has functional properties. A mashed potato serving of 200 g with added soy protein isolate and inulin concentrations of 15?60 g kg provides from 3 to 12 g of soy protein isolate and/or inulin, respectively. Currently, no information is available about the possible texture-modifying effect of this non-ionizable polar carbohydrate in different soy-based food systems. In this study, the effect of the addition of soy protein isolate and inulin blends at different soy protein isolate: inulin ratios on the degree of inulin polymerization and the rheological and structural properties of fresh mashed and frozen/thawed mashed potatoes were evaluated. The inulin chemical structure remained intact throughout the various treatments, and soy protein isolate did not affect inulin composition being a protein compatible with this fructan. Small-strain rheology showed that both ingredients behaved like soft fillers. In the frozen/thawed mashed potatoes samples,0 addition of 30 : 30 and 15 : 60 blend ratios significantly increased elasticity (G value) compared with 0 : 0 control, consequently reducing the freeze/thaw stability conferred by the cryoprotectants. Inulin crystallites caused a significant strengthening effect on soy protein isolate gel. Micrographs revealed that soy protein isolate supports the inulin structure by building up a second fine-stranded network. Thereby, possibility of using soy protein isolate and inulin in combination with mashed potatoes to provide a highly nutritious and healthy product is promising.

Properties and applications of high electron density structures based on InN and related compounds

El objetivo principal del presente trabajo es estudiar y explotar estructuras que presentan un gas bidimensional de electrones (2DEG) basadas en compuestos nitruros con alto contenido de indio. Existen muchas preguntas abiertas, relacionadas con el nitruro de indio y sus aleaciones, algunas de las cuales se han abordado en este estudio. En particular, se han investigado temas relacionados con el análisis y la tecnología del material, tanto para el InN y heteroestructuras de InAl(Ga)N/GaN como para sus aplicaciones a dispositivos avanzados. Después de un análisis de la dependencia de las propiedades del InN con respecto a tratamientos de procesado de dispositivos (plasma y térmicos), el problema relacionado con la formación de un contacto rectificador es considerado. Concretamente, su dificultad es debida a la presencia de acumulación de electrones superficiales en la forma de un gas bidimensional de electrones, debido al pinning del nivel de Fermi. El uso de métodos electroquímicos, comparados con técnicas propias de la microelectrónica, ha ayudado para la realización de esta tarea. En particular, se ha conseguido lamodulación de la acumulación de electrones con éxito. En heteroestructuras como InAl(Ga)N/GaN, el gas bidimensional está presente en la intercara entre GaN y InAl(Ga)N, aunque no haya polarización externa (estructuras modo on). La tecnología relacionada con la fabricación de transistores de alta movilidad en modo off (E-mode) es investigada. Se utiliza un método de ataque húmedo mediante una solución de contenido alcalino, estudiando las modificaciones estructurales que sufre la barrera. En este sentido, la necesidad de un control preciso sobre el material atacado es fundamental para obtener una estructura recessed para aplicaciones a transistores, con densidad de defectos e inhomogeneidad mínimos. La dependencia de la velocidad de ataque de las propiedades de las muestras antes del tratamiento es observada y comentada. Se presentan también investigaciones relacionadas con las propiedades básicas del InN. Gracias al uso de una puerta a través de un electrolito, el desplazamiento de los picos obtenidos por espectroscopia Raman es correlacionado con una variación de la densidad de electrones superficiales. En lo que concierne la aplicación a dispositivos, debido al estado de la tecnología actual y a la calidad del material InN, todavía no apto para dispositivos, la tesis se enfoca a la aplicación de heteroestructuras de InAl(Ga)N/GaN. Gracias a las ventajas de una barrera muy fina, comparada con la tecnología de AlGaN/GaN, el uso de esta estructura es adecuado para aplicaciones que requieren una elevada sensibilidad, estando el canal 2DEG más cerca de la superficie. De hecho, la sensibilidad obtenida en sensores de pH es comparable al estado del arte en términos de variaciones de potencial superficial, y, debido al poco espesor de la barrera, la variación de la corriente con el pH puede ser medida sin necesidad de un electrodo de referencia externo. Además, estructuras fotoconductivas basadas en un gas bidimensional presentan alta ganancia debida al elevado campo eléctrico en la intercara, que induce una elevada fuerza de separación entre hueco y electrón generados por absorción de luz. El uso de metalizaciones de tipo Schottky (fotodiodos Schottky y metal-semiconductormetal) reduce la corriente de oscuridad, en comparación con los fotoconductores. Además, la barrera delgada aumenta la eficiencia de extracción de los portadores. En consecuencia, se obtiene ganancia en todos los dispositivos analizados basados en heteroestructuras de InAl(Ga)N/GaN. Aunque presentando fotoconductividad persistente (PPC), los dispositivos resultan más rápidos con respeto a los valores que se dan en la literatura acerca de PPC en sistemas fotoconductivos. ABSTRACT The main objective of the present work is to study and exploit the two-dimensionalelectron- gas (2DEG) structures based on In-related nitride compounds. Many open questions are analyzed. In particular, technology and material-related topics are the focus of interest regarding both InNmaterial and InAl(Ga)N/GaNheterostructures (HSs) as well as their application to advanced devices. After the analysis of the dependence of InN properties on processing treatments (plasma-based and thermal), the problemof electrical blocking behaviour is taken into consideration. In particular its difficulty is due to the presence of a surface electron accumulation (SEA) in the form of a 2DEG, due to Fermi level pinning. The use of electrochemical methods, compared to standard microelectronic techniques, helped in the successful realization of this task. In particular, reversible modulation of SEA is accomplished. In heterostructures such as InAl(Ga)N/GaN, the 2DEGis present at the interface between GaN and InAl(Ga)N even without an external bias (normally-on structures). The technology related to the fabrication of normally off (E-mode) high-electron-mobility transistors (HEMTs) is investigated in heterostructures. An alkali-based wet-etching method is analysed, standing out the structural modifications the barrier underwent. The need of a precise control of the etched material is crucial, in this sense, to obtain a recessed structure for HEMT application with the lowest defect density and inhomogeneity. The dependence of the etch rate on the as-grown properties is observed and commented. Fundamental investigation related to InNis presented, related to the physics of this degeneratematerial. With the help of electrolyte gating (EG), the shift in Raman peaks is correlated to a variation in surface eletron density. As far as the application to device is concerned, due to the actual state of the technology and material quality of InN, not suitable for working devices yet, the focus is directed to the applications of InAl(Ga)N/GaN HSs. Due to the advantages of a very thin barrier layer, compared to standard AlGaN/GaN technology, the use of this structure is suitable for high sensitivity applications being the 2DEG channel closer to the surface. In fact, pH sensitivity obtained is comparable to the state-of-the-art in terms of surface potential variations, and, due to the ultrathin barrier, the current variation with pH can be recorded with no need of the external reference electrode. Moreover, 2DEG photoconductive structures present a high photoconductive gain duemostly to the high electric field at the interface,and hence a high separation strength of photogenerated electron and hole. The use of Schottky metallizations (Schottky photodiode and metal-semiconductor-metal) reduce the dark current, compared to photoconduction, and the thin barrier helps to increase the extraction efficiency. Gain is obtained in all the device structures investigated. The devices, even if they present persistent photoconductivity (PPC), resulted faster than the standard PPC related decay values.

Comparisson of hydrogen applications for storage and energy vector

For the decades to come can be foreseen that electricity and water will keep be playing a key role in the countries development, both can be considered the most important energy vectors and its control can be crucial for governments, companies and leaders in general. Energy is essential for all human activities and its availability is critical to economic and social development. In particular, electricity, a form of energy, is required to produce goods, to provide medical assistance and basic civic services in education, to assure availability of clean water, to create conducive environment for prosperity and improvement, and to keep an acceptable quality of life. The way in which electricity is generated from different resources varies through the different countries. Nuclear energy controlled within reactors to steam production, gas, fuel-oil and coal fired in power stations, water, solar and wind energy among others are employed, sometimes not very efficiently, to produce electricity. The so call energy mix of an individual country is formed up by the contribution of each resource or form of energy to the electricity generation market of the so country. During the last decade the establishment of proper energy mixes for countries has gained much importance, and energy drivers should enforce long term plans and policies. Hints, reports and guides giving tracks on energy resources contribution are been developed by noticeable organisations like the IEA (International Energy Agency) or the IAEA (International Atomic Energy Agency) and the WEC (World Energy Council). This paper evaluates energy issues the market and countries are facing today regarding energy mix scheduling and panorama. This paper revises and seeks to improve methodology available that are applicable on energy mix plan definition. Key Factors are identified, established and assessed through this paper for the common implementation, the themes driving the future energy mix methodology proposal. Those have a clear influence and are closely related to future environmental policies. Key Factors take into consideration sustainability, energy security, social and economic growth, climate change, air quality and social stability. The strength of the Key Factors application on energy system planning to different countries is contingent on country resources, location, electricity demand and electricity generation industry, technology available, economic situation and prospects, energy policy and regulation

Deriving the full-reducing Krivine machine from the small-step operational semantics of normal order

We derive by program transformation Pierre Crégut s full-reducing Krivine machine KN from the structural operational semantics of the normal order reduction strategy in a closure-converted pure lambda calculus. We thus establish the correspondence between the strategy and the machine, and showcase our technique for deriving full-reducing abstract machines. Actually, the machine we obtain is a slightly optimised version that can work with open terms and may be used in implementations of proof assistants.