Modelling and forecasting fossil fuels, CO2 and electricity prices and their volatilities

In the current uncertain context that affects both the world economy and the energy sector, with the rapid increase in the prices of oil and gas and the very unstable political situation that affects some of the largest raw materials’ producers, there is a need for developing efficient and powerful quantitative tools that allow to model and forecast fossil fuel prices, CO2 emission allowances prices as well as electricity prices. This will improve decision making for all the agents involved in energy issues. Although there are papers focused on modelling fossil fuel prices, CO2 prices and electricity prices, the literature is scarce on attempts to consider all of them together. This paper focuses on both building a multivariate model for the aforementioned prices and comparing its results with those of univariate ones, in terms of prediction accuracy (univariate and multivariate models are compared for a large span of days, all in the first 4 months in 2011) as well as extracting common features in the volatilities of the prices of all these relevant magnitudes. The common features in volatility are extracted by means of a conditionally heteroskedastic dynamic factor model which allows to solve the curse of dimensionality problem that commonly arises when estimating multivariate GARCH models. Additionally, the common volatility factors obtained are useful for improving the forecasting intervals and have a nice economical interpretation. Besides, the results obtained and methodology proposed can be useful as a starting point for risk management or portfolio optimization under uncertainty in the current context of energy markets.

First steps of Roman Cement in Spain

Natural cement was patented in 1796 but it didn’t arrive in Spain until 1835. No one knows exactly where the production started in Spain, because it emerged independently at the same time in many places. Most of these outbreaks are concentrated in the north and northwest of Spain: Basque Country (Zumaya and Rezola) and Catalonia (San Celoní and San Juan de las Abadesas).Natural cement was extensively used to decorate historical buildings during the nineteenth and beginning of twentieth century in Madrid. It was the building material which realised the architects and builders dreams of mass-produced cast elements in a wide variety of styles. Its arrival replaced traditional materials that were used previously (lime, gypsum and hydraulic limes). However, its use was not extended in time, and soon it was replaced by the use of artificial Portland cements. During 20th century this building material disappeared from use. What remains is it’s memory, in thousands and thousands of “stone witnesses” in our cities. Final properties of the cement largely depend on raw materials used and its combustion temperature. However, it was characterised by an easily implementation on facade masonry, fast-setting (about 15 minutes), good resistance , an agreeable structural consistency and colour.This article aims to show first steps, evolution and decay of Natural Cement Industry in Spain and its application in Madrid.

Repercusión medioambiental del uso de la cerámica estructural en España. Energía embebida y huella de carbono

La producción y el transporte a obra de los productos cerámicos de carácter estructural suponen un importante consumo energético, que conlleva la emisión de gases de efecto invernadero a la atmósfera. El objetivo de la presente Tesis es demostrar la existencia de importantes diferencias en el valor del impacto ambiental asociado a los productos de cerámica estructural fabricados en España, y que estas diferencias podrían quedar cuantificadas y reflejadas mediante un análisis de Huella de Carbono y de la Energía Embebida. Se parte de la inexistencia en España, de base de datos contrastada y consensuada, que establezca las cargas medioambientales en función del tipo de producto cerámico a utilizar. Se realiza en la primera parte del estudio una revisión del estado actual de la Huella de Carbono y la Energía Embebida en el campo de los materiales de construcción, y más concretamente en el sector de la cerámica estructural, que sirve para acotar los límites del estudio y justificar el objeto de la Tesis. La investigación se acota a las etapas de producción y transporte a obra de los productos (estudio cuna a puerta con opciones), al considerar que son éstas, a priori, las que tienen una mayor incidencia en el comportamiento ambiental del producto. Siguiendo los pasos definidos en la normativa aplicable (definición del mapa de procesos – límites y alcance – inventario – cálculo y evaluación), se establece un método específico de identificación y cuantificación de las variables que determinan la Huella de Carbono y Energía Embebida de los productos cerámicos, en función de la tipología de producto. La información necesaria (inventario) se obtiene principalmente con recogida de datos “in situ” de fábricas de productos cerámicos, lo que garantiza que la información tratada en este estudio es de primer nivel. La información se complementa/contrasta con fuentes bibliográficas. Se determinan 6 variables con influencia global en el impacto ambiental, 44 variables principales y 39 secundarias, estableciendo las fórmulas de cálculo a partir de dichas variables. Los resultados de cálculo y evaluación determinan que, para unas mismas condiciones de fabricación, las diferencias entre productos cerámicos llegan hasta un 27% para la Huella de Carbono y un 35% para Energía Embebida. La relevancia que alcanza el impacto asociado al transporte del producto a obra puede llegar hasta un 40% del total. El método de cálculo y las fórmulas desarrolladas se integran en una hoja de cálculo, para el cálculo de Huella de Carbono y Energía Embebida de los productos cerámicos, que permite, a su vez, conocer la repercusión medioambiental que tiene la introducción de modificaciones o innovaciones en el proceso de producción o transporte a obra. Así mismo, el trabajo desarrollado ha servido para poner en relieve una serie de problemas y falta de información en el campo de la cerámica estructural y el medioambiente que pueden ser objeto de futuras líneas de investigación, tanto para el sector de la edificación como para la comunidad científica, pudiendo implementar la metodología desarrollada en otras investigaciones. Se considera que la investigación realizada y sus resultados suponen una aportación importante para conocer y reducir el impacto ambiental de los edificios, desde la perspectiva del ciclo de vida y considerando que el impacto ambiental de un edificio comienza desde el momento en que se extraen las materias primas para la fabricación de los materiales con los que se construyen los edificios. ABSTRACT The production and transport of structural ceramic products involves an important energy consumption, which leads to the emission of greenhouse gases into the atmosphere. The objective of the research is to demonstrate the existence of significant differences in the value of the environmental impact of structural ceramic products manufactured in Spain, and these differences could be quantified by the Carbon Footprint and Embodied Energy. It starts from the absence in Spain, of contrasted and agreed databases that establish the environmental loads depending on the type of ceramic product. In the first part of the study reviews the current state of the Carbon Footprint and Embedded Energy in the field of building materials, and more specifically in the field of structural ceramics, which serves to limit the scope of the study and justify the purpose of this Thesis. The Research is bounded to production and transportation stages of (cradle to gate with options), considering they are the stages that have a greater impact on the environmental performance of the product. Following the steps defined in applicable rules (definition of process map - boundaries and scope – inventory analysis- calculation and impact assessment), it sets a specific method for the identification and quantification of the variables that determine the Carbon Footprint and Embedded Energy of structural ceramic products, depending on the type of product. The information (inventory) is given mainly with a data collection in ceramic factories (and in a consultation with the manufactures of the products), ensuring that the information handled in this Thesis is a first rate data. It is established 6 variables with a global influence in the environmental impact, 44 primary and 39 secondary variables, establishing calculation formula from these variables. The results of calculation and assessment determined that, for same manufacturing conditions, the differences between ceramic products reach 27% for Carbon Footprint and 35% for Embodied Energy. The relevance that reaches the impact of transport can reach 40% of the total. The method of calculation and formulas developed are integrated into a simple calculation tool, excel base, to calculate the Carbon Footprint and Embodied Energy of structural ceramic products, which allows, know the environmental impact of changes or innovations in the production process or transport to work. The work also has served to find a problems and gaps in the field of structural ceramics and the environment that may well be the subject of future research, both for the building sector to the scientific community, implementing the methodology developed in other research. It is considered that the research and its results represent an important contribution to understand and reduce the environmental impact of buildings from the perspective of the life cycle, considering that the environmental impact of a building starts from the time that the raw materials are extracted for the manufacture of building materials.

Los residuos de envases y embalajes en edificación residencial. Patrones de generación y estrategias de mejora de su gestión

Uno de los retos a los que se enfrenta la humanidad es la demanda de una sociedad con casi cero residuos: la búsqueda de una economía más eficiente en el uso de los recursos teniendo en cuenta el cambio climático y un abastecimiento sostenible de materias primas que permitan satisfacer las necesidades de una población mundial cada vez mayor, dentro de los límites sostenibles de los recursos naturales del planeta. Abordar este desafío implica la recuperación y reciclaje de materiales para reducir consumos de materias primas y, para ello, debe promoverse la innovación en la prevención y gestión de residuos, como estrategia hacia un desarrollo urbano sostenible. Los envases y embalajes forman parte de la cultura actual, relacionándose con el grado de desarrollo de países y regiones; el sector de la construcción no es ajeno a la problemática y genera un importante volumen de embalajes en las obras que no se gestionan de forma adecuada. El modelo de gestión de Residuos de Construcción Demolición (RCD) actual es poco eficaz, ya que los vertederos siguen recibiendo grandes cantidades de residuos valorizables. La normativa ha conseguido minimizar las prácticas ilegales, pero se comprueba que la gestión actual de los RCD en obra deja en manos de las plantas de tratamiento la misión de separar los residuos según su naturaleza y los datos aportados por las distintas plantas no permiten afirmar el grado de alcance de dicho objetivo, ni el destino de los mismos. Los envases y embalajes son un tipo de residuos que por su naturaleza suponen una fuente de recursos valorizables y por ello están presentes en directivas y leyes, dirigidas fundamentalmente al sector de la alimentación. En el ámbito de la construcción, hasta la fecha, no se habían tratado de forma específica, motivo que justifica este trabajo. Esta Tesis Doctoral tiene como objetivo principal mejorar la gestión de residuos de embalajes procedentes de materiales de construcción. Para ello se estudia un importante conjunto de obras de edificación residencial colectiva de 1173 viviendas, análisis que llevará a conocer los patrones de producción de los Residuos de Envases y Embalajes en Construcción (REEC) e identificar los productos o materiales responsables de su generación. La monitorización realizada, permitirá diseñar estrategias específicas que minimicen la generación de estos residuos y optimicen su valorización. Se ha podido comprobar que el tratamiento particularizado de los REEC puede mejorar los resultados de la gestión del conjunto de RCD, debido a que, al no mezclarse, se elimina un importante agente contaminador de los residuos inertes. Las obras analizadas alcanzan un nivel de segregación in situ muy bajo, y los capítulos de cerramientos e instalaciones suman más del 50% del global de REEC. Particularizando en cada tipo de material, el cartón predomina en los trabajos de electricidad, el plástico en las particiones y la madera en fachadas. Se evalúa la opción del eco-­‐rediseño para uno de los embalajes predominantes, y se identifican estrategias para minimizar su impacto. Se comprueba que el ahorro en la gestión de RCD en caso de impulsar la segregación in situ no es muy significativo en las obras estudiadas, si bien se demuestra que la viabilidad económica es el factor más importante para motivar a las empresas constructoras. Las Administraciones Públicas deberían incentivar la gestión responsable, estableciendo medidas de control en las plantas de tratamiento e implementando en sus obras medidas de gestión de RCD ejemplares para el mercado. Una adecuada planificación de la obra, y formación específica para el personal son medidas que facilitan la segregación in situ y mejoran los resultados. Los promotores, mediante su relación contractual con el resto de agentes, tienen la capacidad de establecer objetivos de reducción, planificación y gestión sostenible de los REEC. Por último, se propone un sistema de gestión de REEC, integrable dentro del Sistema de Gestión de la empresa constructora, que permite evitar que residuos valorizables tales como los envases y embalajes se envíen a vertedero, guiando al sector hacia un futuro más respetuoso, alineado con el desarrollo sostenible. ABSTRACT One of the challenges humanity faces is the demand of an almost zero waste society: the search for a more efficient economy in the use of resources, taking into account climate change and a sustainable supply of raw materials, that meet the needs of an increasing world population within the sustainable limits of the planet's natural resources. Addressing this challenge involves the recovery and recycling of materials to reduce consumption of raw materials, so innovation must therefore be promoted in the prevention and management of waste, as a strategy towards a sustainable urban development. Packaging is part of our current culture and is related to the degree of development of countries and regions; the construction sector is no stranger to this problem and generates a significant amount of packaging waste in the site works, which nowadays is not managed properly. The current Construction Demolition Waste (CDW) management model is ineffective, since landfills continue to receive large amounts of recoverable waste. The legislation has managed to minimize illegal practices, but it has been observed that the current management of CDW in the analysed works leaves the mission of separating waste according to their nature to the plants, and data provided by the latter does not allow for checking the scope of this objective, nor the destiny of the waste. Packaging is a type of waste which, by its nature, represents a source of recoverable resources and is therefore present in directives and laws, focused primarily on the food industry. It has not been specifically treated to date in the construction field, hence the reason that justifies this work. This Thesis aims to improve the management of packaging waste from construction materials. An important set of residential building works with 1173 dwellings is analysed, which leads to knowledge on the production patterns of packaging waste (PW) in the construction industry, and the identification of the products responsible for its generation. The monitorization also allows for the design of specific strategies which minimise the generation of waste and optimize recovery. It has been found that the individualized treatment of PW can improve the results of the management of the whole CDW since, when not mixed, a major pollutant of inert waste is removed. The analysed works reached a very low segregation level and the façades and building services phases account for more than 50% of the overall PW. Focusing on each type of material, cardboard predominates electricity works, plastic on partitions and wood on façades. Eco-­‐redesign is evaluated for one of the predominant packages, and strategies are identified to minimise their impact are . There is evidence that the savings in the CDW management in case of promoting segregation on site are not very significant at the studied works, although economic feasibility is the most important factor to motivate the construction companies. Public Administrations should encourage responsible management, establishing control measures in treatment plants and implementing CDW management exemplary measures on their work sites for the market. A proper planning of the works and specific training for the personnel are measures that facilitate in situ segregation and improve outcomes. The developers, through their contractual relationship with the other agents, have the ability to set reduction targets, planning and sustainable management of PW. Finally, a management system for PW is proposed, integrated within the Management System of the construction company, which aims to avoid that recoverable waste such as packaging is sent to landfill, leading the industry towards a more environmentally friendly future, aligned with sustainable development.

Polymetallic ferromanganese deposits research on the Atlantic Spanish continental margin

Seamounts, submarine banks, volcanoes and undercurrent channels are prominent geomorphic features that have become an important target for minerals research and exploration with the goal of future exploitation. Polymetallic ferromanganese deposits are common types of mineralization on these settings. Co-rich ferromanganese crusts are important as potential resources of Mn and Co, but also Ti, Ni, Tl, REEs, PGEs, and other metals. Many seamounts and channels along the Atlantic Spanish continental margin are known to hold mineral deposits but are poorly studied. This work presents and briefly describes the most recent activities of the Spanish Geological Survey (IGME) on exploration and investigation of ferromanganese deposits along the Atlantic Spanish continental margin. Different submarine areas from the northwestern margin of the Iberian Peninsula to the west off Canary Islands have been surveyed by geophysical, sampling and underwater observations from 89 to 4000 m water depth. The mineral deposits cover a large diversity of submarine geological and geomorphical features: mud volcanoes and diapirs related to hydrocarbon seeps, seamounts associated with hot spot volcanism, hydrothermal vents in active magmatic volcanoes, structural basement highs and banks or contourite channels. Considering the collected dataset, we present the preliminary results of the study of these mineral deposits, including ferromanganese nodules and crusts and phosphate pavements and nodules, which can be considered as potential sources of raw materials.

Factors driving the carbon mineralization priming effect in a sandy loam soil amended with different types of biochar

The effect of biochar on the soil carbon mineral- ization priming effect depends on the characteristics of the raw materials, production method and pyrolysis conditions. The goal of the present study is to evaluate the impact of three different types of biochar on physicochemical properties and CO2 emissions of a sandy loam soil. For this purpose, soil was amended with three different biochars (BI, BII and BIII) at a rate of 8 wt % and soil CO2 emissions were measured for 45 days. BI is produced from a mixed wood sieving from wood chip production, BII from a mixture of paper sludge and wheat husks and BIII from sewage sludge. Cumulative CO2 emissions of biochars, soil and amended soil were well fit to a simple first-order kinetic model with correlation coef- ficients (r 2 ) greater than 0.97. Results show a negative prim- ing effect in the soil after addition of BI and a positive prim- ing effect in the case of soil amended with BII and BIII. These results can be related to different biochar properties such as carbon content, carbon aromaticity, volatile matter, fixed carbon, easily oxidized organic carbon or metal and phenolic substance content in addition to surface biochar properties. Three biochars increased the values of soil field capacity and wilting point, while effects over pH and cation exchange capacity were not observed.

Optimización de la gasificación de lodos de estaciones depuradoras de aguas residuales urbanas para minimizar la formación de alquitranes

La gasificación de lodos de depuración es una alternativa atractiva para generar gases combustibles como H2 y CO. A su vez, estos gases pueden emplearse como materias primas para la obtención de productos químicos orgánicos y combustibles líquidos. Sin embargo, la gasificación no está exenta de problemas como el ligado a la generación de residuos sólidos y alquitrán. El alquitrán en el gas puede ser un inconveniente para emplear el gas como combustible por las obstrucciones y corrosión en los equipos. Dado que las condiciones de gasificación influyen en la producción de alquitrán, este trabajo de investigación se ha centrado en analizar la influencia de parámetros como la temperatura, la carga de alimentación, el tamaño de partícula, el agente gasificante y la utilización de catalizadores en la gasificación en lecho fluidizado de lodos de depuración. Adicionalmente a la medición del efecto de los anteriores parámetros en la producción y composición del alquitrán, también se ha cuantificado su influencia en la producción y composición del gas y en producción del residuo carbonoso. Los resultados muestran que el incremento de la carga de alimentación (kg/h.m2) provoca el descenso de la producción de gas combustible y el incremento del residuo carbonoso y del alquitrán debido a la reducción del tiempo de residencia del gas lo que supone un menor tiempo disponible para las reacciones gas-gas y gas-sólido ligadas a la conversión del alquitrán y del residuo carbonoso en gases combustibles. También se ha comprobado que, el aumento del tamaño de partícula, al incrementar el tiempo de calentamiento de ésta, tiene un efecto similar en los productos de la gasificación que el derivado del incremento en la carga de alimentación. La utilización de una temperatura de gasificación alta (850 ºC), el empleo de aire-vapor como agente gasificante y/o catalizadores primarios como la dolomía consiguen reducir la producción de alquitrán. ABSTRACT Gasification of sewage sludge is an attractive alternative for generating of fuel gases such as H2 and CO. These gases, in turn, can be used as raw materials for the production of organic chemicals and liquid fuel. However, gasification is not without problems as the linked ones to production of char and tar. The tar in the gas can be an inconvenience for to use it as fuel by the problems of blockage and corrosion in the equipments. Since the gasification conditions affect the production of tar, this research has focused on analysing the influence of parameters such as temperature, throughput, the particle size, the gasifying agent and the use of catalysts in the fluidized bed gasification of sewage sludge. In addition to measuring the effect of the above parameters on the production and composition of the tar, it has also been quantified their influence on the yield and composition of the gas and char production. The results show that higher throughput (kg/h.m2) leads to a reduction of fuel gas production and an increase in the production of char and tar, this owes to a lower of gas residence time or what is the same thing less time available for gas-solid and gas-gas reactions attached to the conversion of tar and char to fuel gases. There has also been proven that the rising in particle size, by the increasing heating time of it, has a similar effect in the products of gasification that the results by the rise in the throughput. The applications a high gasification temperature (850 ° C), the use of air-steam as gasifying agent and/or dolomite as primary catalysts are able to reduce the production of tar.

Proyecto para la instalación de una planta de tratamiento de residuos de construcción y demolición en la comunidad de Madrid

La problemática actual de las canteras en la cercanía de las grandes ciudades, debido a la escasez de yacimientos y a las restricciones medioambientales, están poniendo en graves problemas el abastecimiento de áridos naturales y encareciendo su coste. El proyecto realizado responde a la actual necesidad de los países del mundo desarrollado por buscar soluciones a los problemas de abastecimiento de materias primas para la construcción en las zonas urbanizadas. La dependencia de nuestra sociedad hacia los recursos naturales y la consideración de su importancia hacen que se deban aprovechar al máximo, ya sea reciclando, reutilizando o revalorizando. Este proyecto está centrado en los residuos utilizados en el sector de la construcción y la viabilidad de su reutilización. Hemos evaluado la situación y la legislación acerca de la posibilidad de reciclar los materiales de la construcción para volverlos a introducir en el mercado; llevando a cabo una aplicación práctica en la Comunidad de Madrid. El proyecto se complementa con el diseño y estudio de viabilidad de una instalación de reciclaje de residuos de la construcción y demolición en este micromercado. ABSTRACT The current problems of the quarries in the vicinity of large cities, due to the scarcity of deposits and environmental restrictions are putting in serious trouble supplying natural aggregates and more expensive cost. The project undertaken reflects the current need for developed countries to seek solutions to the problems of supply of raw materials for construction in urbanized areas worldwide. The dependence of our society towards natural resources and consideration of its importance that should be made to maximize either by recycling , reusing or revalued. This project is focused on the waste used in the construction sector and feasibility of reuse. We have assessed the situation and legislation about the possibility of recycling construction materials for re- entering the market ; carrying out a practical application in the Community of Madrid. The project complements the design and feasibility study of a facility for recycling construction waste and demolition in this micro market

Determinación de las características acústicas de materiales de construcción de Ecuador - Ladrillo artesanal e industrial

En el presente trabajo se plantea el estudio de las características acústicas del ladrillo artesanal e industrial fabricado en Ecuador, considerando las características particulares respecto a la calidad de la materia prima, además del hecho de que a nivel artesanal su producción no está regularizada, si bien existen una serie de reglamentos no siempre son acatados por el productor artesanal, lo que hace que presente propiedades particulares. La idea principal de este trabajo es generar datos referenciales e iniciales, sobre las propiedades acústicas del ladrillo artesanal e industrial ya que en Ecuador, no existe ningún estudio de esta naturaleza sobre el tema. Además de crear los mecanismos necesarios para una posible ampliación del estudio a otros materiales propios de Ecuador que permitan generar una base de datos sobre sus propiedades acústicas. Otro aspecto importante sobre esta investigación es el familiarizarse con el uso de técnicas de medición, manejo de equipamiento y software diverso, del manejo y comparación de normativa. ABSTRACT. The purpose of this paper is the study of the acoustic characteristics of artisanal and industrial brick manufactured in Ecuador, considering the particular characteristics regarding the quality of raw materials, besides the fact that artisanal production level is unregulated, although there are a number of regulations are not always complied with by the artisan producer, which makes this particular properties. The main idea of this paper is to generate reference and baseline data on the acoustic properties of artisanal and industrial brick as in Ecuador, there is no study of this nature on the subject. In addition to creating the necessary mechanisms for a possible extension of the study to other materials from Ecuador that will generate a database on its acoustic properties. Another important aspect of this research is to get familiar with the use of measurement techniques, equipment and miscellaneous management software, management and comparison of legislation.

Life cycle assessment of concentrated solar power (CSP) and the influence of hybridising with natural gas

Purpose Concentrating Solar Power (CSP) plants based on parabolic troughs utilize auxiliary fuels (usually natural gas) to facilitate start-up operations, avoid freezing of HTF and increase power output. This practice has a significant effect on the environmental performance of the technology. The aim of this paper is to quantify the sustainability of CSP and to analyse how this is affected by hybridisation with different natural gas (NG) inputs. Methods A complete Life Cycle (LC) inventory was gathered for a commercial wet-cooled 50 MWe CSP plant based on parabolic troughs. A sensitivity analysis was conducted to evaluate the environmental performance of the plant operating with different NG inputs (between 0 and 35% of gross electricity generation). ReCiPe Europe (H) was used as LCA methodology. CML 2 baseline 2000 World and ReCiPe Europe E were used for comparative purposes. Cumulative Energy Demands (CED) and Energy Payback Times (EPT) were also determined for each scenario. Results and discussion Operation of CSP using solar energy only produced the following environmental profile: climate change 26.6 kg CO2 eq/KWh, human toxicity 13.1 kg 1,4-DB eq/KWh, marine ecotoxicity 276 g 1,4-DB eq/KWh, natural land transformation 0.005 m2/KWh, eutrophication 10.1 g P eq/KWh, acidification 166 g SO2 eq/KWh. Most of these impacts are associated with extraction of raw materials and manufacturing of plant components. The utilization NG transformed the environmental profile of the technology, placing increasing weight on impacts related to its operation and maintenance. Significantly higher impacts were observed on categories like climate change (311 kg CO2 eq/MWh when using 35 % NG), natural land transformation, terrestrial acidification and fossil depletion. Despite its fossil nature, the use of NG had a beneficial effect on other impact categories (human and marine toxicity, freshwater eutrophication and natural land transformation) due to the higher electricity output achieved. The overall environmental performance of CSP significantly deteriorated with the use of NG (single score 3.52 pt in solar only operation compared to 36.1 pt when using 35 % NG). Other sustainability parameters like EPT and CED also increased substantially as a result of higher NG inputs. Quasilinear second-degree polynomial relationships were calculated between various environmental performance parameters and NG contributions. Conclusions Energy input from auxiliary NG determines the environmental profile of the CSP plant. Aggregated analysis shows a deleterious effect on the overall environmental performance of the technology as a result of NG utilization. This is due primarily to higher impacts on environmental categories like climate change, natural land transformation, fossil fuel depletion and terrestrial acidification. NG may be used in a more sustainable and cost-effective manner in combined cycle power plants, which achieve higher energy conversion efficiencies.

Modelización de procesos de soldadura (GMAW y GTAW) de la aleación de magnesio AZ31B. Estudio y análisis del comportamiento de este tipo de uniones soldadas frente a la corrosión en medios salinos

El magnesio y sus aleaciones representan un interesante campo de investigación dentro de la ingeniería de materiales debido a los retos que plantean tanto su conformabilidad como durabilidad. Las características físicas y mecánicas del magnesio y sus aleaciones los convierten en materiales de gran interés desde el punto de vista industrial al tratarse de uno de los materiales más abundantes y ligeros en un mundo en el que día a día los recursos y materias primas son más escasos por lo que el acceso a materiales abundantes y ligeros que permitan economizar el uso de energía cobrará mayor importancia en el futuro. En la coyuntura actual es por tanto necesario revisar procesos y procedimientos, investigando y tratando de ampliar desde este punto de vista si es posible mejorar los procedimientos de fabricación de los materiales disponibles actualmente o el desarrollo de nuevos, mejores que los anteriores, que permitan ayudar a la sostenibilidad del planeta. El magnesio, pese a ser un material muy abundante y relativamente barato, presenta una serie de inconvenientes que limitan de manera muy seria su aplicación industrial, su alta reactividad en presencia de oxígeno y su mal comportamiento frente a la corrosión así como limitaciones en su conformabilidad han estado limitando su uso y aplicaciones, los investigaciones dentro del campo de la metalurgia física de este material y el desarrollo de nuevas aleaciones han permitido su empleo en múltiples aplicaciones dentro de la industria aeroespacial, militar, automovilística, electrónica, deportiva y médica. La motivación para esta tesis doctoral ha sido tratar de aportar más luz sobre el comportamiento de una de las aleaciones comerciales base magnesio más empleadas, la AZ31B, tratando de modelizar como le afectan los procesos de soldadura y estudiando desde un punto de vista experimental como se ve modificada su microestructura, su comportamiento mecánico y su resistencia frente a la corrosión. Aunque en un principio se pensó en el empleo de métodos electroquímicos para el estudio de la corrosión de estos materiales, rápidamente se decidió prescindir de su uso dada la dificultad observada tanto durante los trabajos de investigación de esta Tesis como los encontrados por otros investigadores. Mediante microdurezas se han caracterizado mecánicamente las soldaduras de aleación de magnesio tipo AZ31 en función de diferentes materiales de aporte, observándose que el empleo de las aleaciones con mayor contenido de aluminio y zinc no contribuye a una mejora significativa de las propiedades mecánicas. Se han podido establecer correlaciones entre los modelos de simulación desarrollados y las microestructuras resultantes de los procesos reales de soldadura que permiten definir a priori que estructuras se van a obtener. De igual forma ha sido posible completar un estudio micrográfico y químico completo de las diferentes fases y microconstituyentes originados durante los procesos de soldadura, gracias a estos resultados se ha propuesto como hipótesis una explicación que justifica el comportamiento frente a la corrosión de estas aleaciones una vez soldadas. Los ensayos de corrosión realizados han permitido determinar correlaciones matemáticas que indican las velocidades de corrosión esperables de este tipo de aleaciones. Desde el punto de vista del diseño, los resultados obtenidos en este trabajo permitirán a otros investigadores y diseñadores tomar decisiones a la hora de decidir qué materiales de aporte emplear junto con las implicaciones que conllevan desde el punto de vista metalúrgico, mecánico o corrosivo las diferentes alternativas. Por último indicar que gracias al trabajo desarrollado se han definido modelos matemáticos para predecir el comportamiento frente a la corrosión de estas aleaciones, se han determinado las posibles causas y mecanismos por las que se gobierna la corrosión en la soldadura de chapas de aleación AZ31B y los motivos por los que se debe considerar el empleo de un material de aporte u otro. Los modelos de simulación desarrollados también han ayudado a comprender mejor la microestructura resultante de los procesos de soldadura y se han determinado que fases y microconstituyentes están presentes en las soldaduras de estas aleaciones. ABSTRACT Magnesium and its alloys represent and interesting research field in the material science due to the challenges of their fabrication and durability. The physical and mechanical properties of magnesium and its alloys make them a very interesting materials from and industrial point of view being one of the most abundant and lightest materials in a world in which day by day the lacking of resources and raw materials is more important, the use of light materials which allow to save energy will become more important in a near future. So that it is necessary to review processes and procedures, investigating and trying to improve current fabrication procedures and developing new ones, better than the former ones, in order to help with the sustainability of the planet. Although magnesium is a very common and relatively cheap material, it shows some inconveniences which limit in a major way their industrial application; its high reactivity in presence of oxygen, its poor corrosion resistance and some manufacturing problems had been limiting their use and applications, metallurgical investigations about this material and the development of new alloys have allowed its use in multiple applications in the aerospacial, military, automobile, electronics, sports and medical industry. The motivation for this thesis has been trying to clarify the behavior of one most used commercial base magnesium alloys, the AZ31, trying to modeling how its affected by thermal cycles of the welding process and studying from an experimental point of view how its microstructure is modified and how these modifications affect its mechanical behavior and corrosion resistance. Although at the beginning of this works it was though about the using of electrochemical techniques to evaluate the corrosion of these materials, rapidly it was decided not to use them because of the difficulty observed by during this research and by other investigators. The results obtained in this thesis have allowed to characterize mechanically AZ31 magnesium welding alloys considering different filler metals, according to this study using filler metals with a high content of aluminum and zinc does not represent an important improve It has been possible to establish correlations between simulation models and the resultant microstructures of the real melting processes originated during welding processes which allow to predict the structures which will be obtained after the welding. In addition to that it is possible to complete a complete micrographic and chemical analysis of the different phases and microconstituents created during welding, due to these results and hypothesis to explain the corrosion behavior of these welded alloys. Corrosion tests carried out have allowed defining mathematical correlations to predict corrosion rates of this kind of alloys. From a designing point of view, the results obtained in this work will let other investigators and designers to make decisions taking into account which implications have the different options from a metallurgical, mechanic and corrosive point of view. Finally we would like to indicate that thanks to this work it has been possible to define mathematical models to predict the corrosion behavior, the causes and the mechanism of this corrosion in the AZ31 welding sheets have been also determined and the reasons for using of one filler metal or another, the developed simulation models have also help to get a better understanding of the result microstructure determining the phases and the microconstituents present in the welding of this alloys.

Aplicación integral en construcción de materiales eco-eficientes con incorporación de cenizas de biomasa

El empleo de biomasa como combustible para la generación de bio-energía va en aumento en la actualidad, debido a su impacto medioambiental nulo en cuanto a las emisiones de CO2. Por lo tanto la generación de cenizas de biomasa, residuo de la producción de esta energía, constituye un problema medioambiental con un claro impacto social y económico. Este tipo de ceniza tiene contenidos en óxidos que la hacen atractiva para su empleo como sustituto parcial del cemento Portland, lo cual proporciona una salida eco-eficiente a este residuo, reduciendo al mismo tiempo la emisión de gases de efecto invernadero asociada a la fabricación del cemento. Esta investigación se centra en el desarrollo de nuevos e innovadores materiales base-cemento eco-eficientes que incorporan ceniza de biomasa para su aplicación integral en construcción. Para ello, se emplea una ceniza de biomasa (CB) procedente de un combustor de lecho fluidizado, cuya biomasa de combustión es principalmente restos de corteza de eucalipto, suministrada por el grupo ENCE-Navia (Asturias). El trabajo desarrollado en la presente tesis doctoral, tiene como primera fase la caracterización de esta ceniza y el análisis de viabilidad de su valorización en materiales base-cemento. Dentro de este análisis, se propone la activación de la ceniza CB mediante tratamiento hidrotermal (TH) en diferentes condiciones de medio activante, temperatura y tiempo de proceso, con el objetivo de favorecer la formación de fases hidratadas que potencien la valorización de la ceniza en el campo de los materiales de construcción. Como fase hidratada de interés se obtiene la fase tobermorita (Ca2.25(Si3O7.5(OH)1.5)(H2O)), precursora del gel C-S-H, responsable del desarrollo de resistencias mecánicas en los materiales base-cemento. El proceso de TH se optimiza para la síntesis más eficiente de esta fase. El estudio posterior de las propiedades mecánicas y micro-estructurales de pastas de cemento eco-eficientes que incorporan la ceniza CB y la ceniza tratada hidrotermalmente, CB-TH, confirma una mayor viabilidad de incorporación de la ceniza CB como sustituto parcial del cemento Portland. Como siguiente paso en el desarrollo de estos innovadores materiales base-cemento eco-eficientes se amplía el estudio multi-escalar de los materiales que incorporan CB mediante diferentes ensayos físico-mecánicos y de durabilidad. Los resultados indican que la presencia de la ceniza de biomasa no tiene efectos negativos sobre las propiedades físicas de los morteros eco-eficientes estudiados. Sin embargo, la adición de CB proporciona una mejor durabilidad del material al producir modificaciones de la microestructura que dificultan el transporte de agentes agresivos. Por otro lado, los morteros con un 10 y 20% de sustitución parcial de cemento por la ceniza de biomasa CB (CB-10 y CB-20) presentan una resistencia a compresión de 53.3 y 50.5 MPa a 28 días de curado, respectivamente. Estos morteros son comparables con un cemento Portland tradicional tipo CEM I de clase de resistencia 42.5 R. Por último, y con el fin de proporcionar la apertura de estos nuevos cementos eco-eficientes al mercado en el campo de los materiales de construcción, se estudian propiedades concretas relacionadas con diferentes tipos de aplicaciones. Concretamente se estudian en detalle las propiedades relativas a la aplicación en baldosas de mortero y los resultados indican unas prestaciones del material eco-eficiente con incorporación de CB similares o mejoradas con respecto al cemento Portland. Se analiza también la viabilidad de aplicación estructural de los cementos eco-eficientes desarrollados mediante el estudio de la adherencia al acero, que resulta similar a la del material de referencia. En cuanto a los resultados de extracción y caracterización de la fase acuosa de los poros, en todas las matrices eco-eficientes se obtiene un pH que garantiza la pasivación de la armadura. Sin embargo, el alto contenido en cloruros de dicha fase acuosa sugiere la conveniencia de realizar un análisis más detallado para la aplicación de los nuevos materiales eco-eficientes en hormigón armado. Se comprueba que todas las matrices que incorporan CB en porcentajes entre un 10 y un 90%, se pueden considerar adecuadas como nuevos materiales de construcción más eco-eficientes en aplicaciones con distintos niveles de exigencias mecánicas y sin problemas ambientales asociados con procesos de lixiviación. Con el presente trabajo de investigación se completan los objetivos iniciales de la tesis, con la obtención de nuevos e innovadores materiales base-cemento eco-eficientes que incorporan cenizas de biomasa (CB) con aplicación integral en el campo de la construcción. ABSTRACT The use of biomass as a fuel for the generation of bio-energy is increasing nowadays, due to its zero environmental impact in terms of CO2 emissions. Therefore the generation of biomass ash, a by-product of this energy, is an environmental problem with a clear social and economic impact. This type of ash contains oxides that make it attractive to be used as a partial replacement of Portland cement, providing an eco-efficient solution to this residue, while reducing the emission of greenhouse gases associated with the production of cement. The present research is focused on the development of new and innovative eco-efficient cement-based materials that incorporate biomass ash for their comprehensive application in construction. For this purpose a biomass ash (CB) is used from a fluidized bed forest combustor mainly fed with the bark of eucalyptus trees, provided by the ENCE-Navia (Asturias) group. The work includes in the first stage the characterization of the raw materials and the analysis of viability of their valorization in cement-based materials. Within this analysis, the activation of the ash is proposed by hydrothermal treatment (HT) in different conditions of activation medium, temperature and process duration, aiming an enhanced formation of hydrated phases to improve the ash valorization in the construction materials field. As an interesting hydrated phase, the tobermorite (Ca2.25(Si3O7.5(OH)1.5)(H2O)) is obtained from the process. This phase is considered as a precursor of the gel C-S-H, responsible for the development of mechanical strength in cement-based materials. HT process is optimized for the most efficient synthesis of tobermorite. The analysis of mechanical and microstructural properties of eco-efficient cement pastes incorporating CB ash and hydrothermally treated ash, CB-TH, confirms an improved viability of incorporation of CB ash as a partial replacement for Portland cement in the case. As a next step in the development of these innovative eco-efficient cement-based materials, a multiscale study of the materials that incorporate CB by different physical-mechanical and durability tests is carried out. The results indicate that the presence of biomass ash does not give rise to negative effects on the physical properties of the eco-efficient mortars analyzed. Nevertheless, the addition of CB produces a better durability performance due to microstructural modifications that hinder the transport of aggressive agents through the material. Moreover, mortars with a 10% and 20% of partial substitution of cement by the CB biomass ash (CB-10 and CB-20) show a compressive resistance of 53.3 and 50.5 MPa at 28 days of curing, respectively. These mortars are comparable to an ordinary Portland cement type CEM I with a resistance class of 42.5R. Finally, and in order to provide the opening of these new eco-efficient cement to the market in the field of construction materials, certain properties specifically related to different types of applications are studied. Among these, the properties concerning the application in mortar tiles are analyzed and the results indicate a similar, or even better performance of the eco-efficient mortar that incorporates CB, with respect to Portland cement. The viability of structural application of the developed eco-efficient cement is also performed considering the study of the adhesion to steel, with results similar to those of the reference material. Regarding the results of extraction and analysis of the aqueous phase of the pores, a pH value guaranteeing reinforcement passivation is obtained for all the eco-efficient matrices. However, high chloride content is obtained suggesting the suitability of a more detailed study to evaluate the application of these new eco-efficient materials in reinforced concrete. It is established that all the matrices incorporating CB in percentages between 10 and 90% may be considered adequate as new more eco-efficient construction materials in applications with different levels of mechanical demand and without environmental problems associated to leaching processes. In this research the initial objectives of the thesis are fulfilled by obtaining new and innovative eco-efficient cement-based materials that incorporate biomass ashes (CB) with comprehensive application in the construction field.

Innovative analytical strategies for the development of sensor devices and mass spectrometry methods

Il lavoro presentato in questa tesi di Dottorato è incentrato sullo sviluppo di strategie analitiche innovative basate sulla sensoristica e su tecniche di spettrometria di massa in ambito biologico e della sicurezza alimentare. Il primo capitolo tratta lo studio di aspetti metodologici ed applicativi di procedure sensoristiche per l’identificazione e la determinazione di biomarkers associati alla malattia celiaca. In tale ambito, sono stati sviluppati due immunosensori, uno a trasduzione piezoelettrica e uno a trasduzione amperometrica, per la rivelazione di anticorpi anti-transglutaminasi tissutale associati a questa malattia. L’innovazione di questi dispositivi riguarda l’immobilizzazione dell’enzima tTG nella conformazione aperta (Open-tTG), che è stato dimostrato essere quella principalmente coinvolta nella patogenesi. Sulla base dei risultati ottenuti, entrambi i sistemi sviluppati si sono dimostrati una valida alternativa ai test di screening attualmente in uso per la diagnosi della celiachia. Rimanendo sempre nel contesto della malattia celiaca, ulteriore ricerca oggetto di questa tesi di Dottorato, ha riguardato lo sviluppo di metodi affidabili per il controllo di prodotti “gluten-free”. Il secondo capitolo tratta lo sviluppo di un metodo di spettrometria di massa e di un immunosensore competitivo per la rivelazione di prolammine in alimenti “gluten-free”. E’ stato sviluppato un metodo LC-ESI-MS/MS basato su un’analisi target con modalità di acquisizione del segnale selected reaction monitoring per l’identificazione di glutine in diversi cereali potenzialmente tossici per i celiaci. Inoltre ci si è focalizzati su un immunosensore competitivo per la rivelazione di gliadina, come metodo di screening rapido di farine. Entrambi i sistemi sono stati ottimizzati impiegando miscele di farina di riso addizionata di gliadina, avenine, ordeine e secaline nel caso del sistema LC-MS/MS e con sola gliadina nel caso del sensore. Infine i sistemi analitici sono stati validati analizzando sia materie prime (farine) che alimenti (biscotti, pasta, pane, etc.). L’approccio sviluppato in spettrometria di massa apre la strada alla possibilità di sviluppare un test di screening multiplo per la valutazione della sicurezza di prodotti dichiarati “gluten-free”, mentre ulteriori studi dovranno essere svolti per ricercare condizioni di estrazione compatibili con l’immunosaggio competitivo, per ora applicabile solo all’analisi di farine estratte con etanolo. Terzo capitolo di questa tesi riguarda lo sviluppo di nuovi metodi per la rivelazione di HPV, Chlamydia e Gonorrhoeae in fluidi biologici. Si è scelto un substrato costituito da strips di carta in quanto possono costituire una valida piattaforma di rivelazione, offrendo vantaggi grazie al basso costo, alla possibilità di generare dispositivi portatili e di poter visualizzare il risultato visivamente senza la necessità di strumentazioni. La metodologia sviluppata è molto semplice, non prevede l’uso di strumentazione complessa e si basa sull’uso della isothermal rolling-circle amplification per l’amplificazione del target. Inoltre, di fondamentale importanza, è l’utilizzo di nanoparticelle colorate che, essendo state funzionalizzate con una sequenza di DNA complementare al target amplificato derivante dalla RCA, ne permettono la rivelazione a occhio nudo mediante l’uso di filtri di carta. Queste strips sono state testate su campioni reali permettendo una discriminazione tra campioni positivi e negativi in tempi rapidi (10-15 minuti), aprendo una nuova via verso nuovi test altamente competitivi con quelli attualmente sul mercato.

Determinação de biomarcadores de aflatoxina B1 e aplicabilidade na avaliação da eficiência de adsorventes em frangos de corte

As aflatoxinas são metabólitos secundários produzidos por fungos toxigênicos das espécies Aspergillus flavus, A. parasiticus e A. nomius. São amplamente encontradas em matérias-primas de rações animais, em especial o milho, e têm a capacidade de levar a quadros clínicos agudos ou crônicos de aflatoxicose, caracterizados por, desde a morte por hepatite aguda até a diminuição do desempenho zootécnico por diminuição de peso ou consumo de ração. A aflatoxina B1 tem sido considerada o metabólito mais perigoso, uma vez que possui alto poder hepatotóxico, além de ser mutagênica e carcinogênica. Atualmente a ciência trabalha rumo à descoberta de substâncias que sejam indicadoras confiáveis de contaminação por componentes tóxicos em homens e em animais, os chamados biomarcadores, que medem uma mudança celular, biológica ou molecular em um meio biológico (tecidos humanos, células ou fluídos) que fornecem informação a respeito de uma doença ou exposição a uma determinada substância. Sua detecção pode auxiliar na identificação, no diagnóstico e no tratamento de indivíduos afetados que podem estar sob risco, mas ainda não exibem os sintomas. Sendo assim, com o auxílio de análises que confirmem a patogenicidade da aflatoxina B1 (determinação da atividade de enzimas hepáticas, da avaliação da função renal, de hematologia, da dosagem de minerais séricos e da avaliação de desempenho zootécnico), o objetivo deste trabalho foi avaliar a aplicabilidade da determinação de resíduos hepáticos de aflatoxinas e do aduto sérico AFB1-lisina na avaliação da eficiência de adsorventes em frangos de corte. Utilizou-se 240 pintos de 1 dia, machos, de linhagem Cobb 500®, distribuídos aleatoriamente em 4 dietas experimentais: Controle Negativo: Ração Basal (RB); RB + 0,5% de adsorvente ((aluminosilicato de cálcio e sódio hidratado/HSCAS); RB + 0,5% de adsorvente + 500 µg de AFB1/kg de ração e; RB + 500 µg de AFB1/kg de ração.Os resultados experimentais mostram que o efeito deletério da AFB1, na concentração utilizada, é mais pronunciado que os efeitos protetores do HSCAS sobre os parâmetros de saúde dos animais. Não houve ação efetiva do adsorvente utilizado sobre quase nenhuma variável estudada, apenas para a redução das lesões histopatológicas em fígado, na redução da concentração de gama-glutamiltransferase (GGT), fósforo e aumento da contagem de hemáceas aos 21 dias de idade. Porém, influenciou positivamente a redução de resíduos hepáticos de aflatoxina G1 aos 21 dias e as concentrações de AFB1-lisina sérica aos 21 e aos 42 dias de idade. Estes dados são importantes porque permite concluir que, embora sintomatologicamente o HSCAS não tenha exercido função efetiva, molecularmente foi capaz de mostrar de eficácia sobre os alguns biomarcadores de aflatoxinas no organismo das aves

Competitividade da cadeia produtiva do Arapaima gigas, o pirarucu da Amazônia brasileira

Com um quinto da água doce do planeta, o sistema fluvial da Amazônia apresenta um enorme potencial para piscicultura. De acordo com a FAO, em função das suas condições geográficas, o Brasil é um dos poucos países que tem condições de atender à crescente demanda mundial, podendo tornar-se um dos maiores produtores de peixes do mundo. A observação desse potencial amazônico motivou o desenvolvimento desta pesquisa que se debruça sobre a questão da competitividade da cadeia produtiva de Arapaima gigas, o pirarucu da Amazônia brasileira. As pesquisas de campo levaram ao mapeamento de duas cadeias: a cadeia extrativista e a piscicultura. A abordagem sistêmica permitiu a verificação das características dos atores e as bases sob as quais as transações se estabelecem. À luz da teoria das restrições foram identificados os gargalos que impedem a competitividade do sistema, inclusive alertando para os recursos com restrição de capacidade. Comprovou-se que a falta de uma cadeia produtiva devidamente organizada pode provocar graves prejuízos a determinados elos, enquanto outros membros aproveitam-se de ações oportunistas para ampliar suas margens de lucro. Da mesma forma, a ausência de uma cadeia produtiva completa impede a fixação do valor gerado na região de origem das matérias-primas. No entanto, também foi possível comprovar que há possibilidade de desenvolver o extrativismo atribuindo valor econômico aos recursos naturais e gerando renda para a comunidade local. Além de apresentar o panorama do setor na região delimitada, este estudo culminou em reflexões capazes de orientar políticas públicas para o desenvolvimento de cadeias produtivas completas na região da Amazônia brasileira.