Hybridizing concentrated solar power (CSP) with biogas and biomethane as an alternative to natural gas: Analysis of environmental performance using LCA

Concentrating Solar Power (CSP) plants typically incorporate one or various auxiliary boilers operating in parallel to the solar field to facilitate start up operations, provide system stability, avoid freezing of heat transfer fluid (HTF) and increase generation capacity. The environmental performance of these plants is highly influenced by the energy input and the type of auxiliary fuel, which in most cases is natural gas (NG). Replacing the NG with biogas or biomethane (BM) in commercial CSP installations is being considered as a means to produce electricity that is fully renewable and free from fossil inputs. Despite their renewable nature, the use of these biofuels also generates environmental impacts that need to be adequately identified and quantified. This paper investigates the environmental performance of a commercial wet-cooled parabolic trough 50 MWe CSP plant in Spain operating according to two strategies: solar-only, with minimum technically viable energy non-solar contribution; and hybrid operation, where 12 % of the electricity derives from auxiliary fuels (as permitted by Spanish legislation). The analysis was based on standard Life Cycle Assessment (LCA) methodology (ISO 14040-14040). The technical viability and the environmental profile of operating the CSP plant with different auxiliary fuels was evaluated, including: NG; biogas from an adjacent plant; and BM withdrawn from the gas network. The effect of using different substrates (biowaste, sewage sludge, grass and a mix of biowaste with animal manure) for the production of the biofuels was also investigated. The results showed that NG is responsible for most of the environmental damage associated with the operation of the plant in hybrid mode. Replacing NG with biogas resulted in a significant improvement of the environmental performance of the installation, primarily due to reduced impact in the following categories: natural land transformation, depletion of fossil resources, and climate change. However, despite the renewable nature of the biofuels, other environmental categories like human toxicity, eutrophication, acidification and marine ecotoxicity scored higher when using biogas and BM.

Some considerations on the compile-time analysis of constraint logic programs

This paper discusses some issues which arise in the dataflow analysis of constraint logic programming (CLP) languages. The basic technique applied is that of abstract interpretation. First, some types of optimizations possible in a number of CLP systems (including efficient parallelization) are presented and the information that has to be obtained at compile-time in order to be able to implement such optimizations is considered. Two approaches are then proposed and discussed for obtaining this information for a CLP program: one based on an analysis of a CLP metainterpreter using standard Prolog analysis tools, and a second one based on direct analysis of the CLP program. For the second approach an abstract domain which approximates groundness (also referred to as "definiteness") information (i.e. constraint to a single valué) and the related abstraction functions are presented.

Aspectos de la medición dinámica instantánea de emisiones de motores. Aplicación al desarrollo de un equipo portátil y una metodología para estudios de contaminación de vehículos en tráfico real.

Esta Tesis Doctoral se encuadra en el ámbito de la medida de emisiones contaminantes y de consumo de combustible en motores de combustión interna alternativos cuando se utilizan como plantas de potencia para propulsión de vehículos ligeros de carretera, y más concretamente en las medidas dinámicas con el vehículo circulando en tráfico real. En este ámbito, el objetivo principal de la Tesis es estudiar los problemas asociados a la medición en tiempo real con equipos embarcados de variables medioambientales, energéticas y de actividad, de vehículos ligeros propulsados por motores térmicos en tráfico real. Y como consecuencia, desarrollar un equipo y una metodología apropiada para este objetivo, con el fin de realizar consiguientemente un estudio sobre los diferentes factores que influyen sobre las emisiones y el consumo de combustible de vehículos turismo en tráfico real. La Tesis se comienza realizando un estudio prospectivo sobre los trabajos de otros autores relativos al desarrollo de equipos portátiles de medida de emisiones (Portable Emission Measurement Systems – PEMS), problemas asociados a la medición dinámica de emisiones y estudios de aplicación en tráfico real utilizando este tipo de equipos. Como resultado de este estudio se plantea la necesidad de disponer de un equipo específicamente diseñado para ser embarcado en un vehículo que sea capaz de medir en tiempo real las concentraciones de emisiones y el caudal de gases de escape, al mismo tiempo que se registran variables del motor, del vehículo y del entorno como son la pendiente y los datos meteorológicos. De esta forma se establecen las especificaciones y condiciones de diseño del equipo PEMS. Aunque al inicio de esta Tesis ya existían en el mercado algunos sistemas portátiles de medida de emisiones (PEMS: Portable Emissions Measurement Systems), en esta Tesis se investiga, diseña y construye un nuevo sistema propio, denominado MIVECO – PEMS. Se exponen, discuten y justifican todas las soluciones técnicas incorporadas en el sistema que incluyen los subsistema de análisis de gases, subsistemas de toma de muestra incluyendo caudalímetro de gases de escape, el subsistema de medida de variables del entorno y actividad del vehículo y el conjunto de sistemas auxiliares. El diseño final responde a las hipótesis y necesidades planteadas y se valida en uso real, en banco de rodillos y en comparación con otro equipos de medida de emisiones estacionarios y portátiles. En esta Tesis se presenta también toda la investigación que ha conducido a establecer la metodología de tratamiento de las señales registradas en tiempo real que incluye la sincronización, cálculos y propagación de errores. La metodología de selección y caracterización de los recorridos y circuitos y de las pautas de conducción, preparación del vehículo y calibración de los equipos forma también parte del legado de esta Tesis. Para demostrar la capacidad de medida del equipo y el tipo de resultados que pueden obtenerse y que son útiles para la comunidad científica, y las autoridades medioambientales en la parte final de esta Tesis se plantean y se presentan los resultados de varios estudios de variables endógenas y exógenas que afectan a las emisiones instantáneas y a los factores de emisión y consumo (g/km) como: el estilo de conducción, la infraestructura vial, el nivel de congestión del tráfico, tráfico urbano o extraurbano, el contenido de biocarburante, tipo de motor (diesel y encendido provocado), etc. Las principales conclusiones de esta Tesis son que es posible medir emisiones másicas y consumo de motores de vehículos en uso real y que los resultados permiten establecer políticas de reducción de impacto medio ambiental y de eficiencia energética, pero, se deben establecer unas metodologías precisas y se debe tener mucho cuidado en todo el proceso de calibración, medida y postratamientos de los datos. Abstract This doctoral thesis is in the field of emissions and fuel consumption measurement of reciprocating internal combustion engines when are used as power-trains for light-duty road vehicles, and especially in the real-time dynamic measurements procedures when the vehicle is being driven in real traffic. In this context, the main objective of this thesis is to study the problems associated with on-board real-time measuring systems of environmental, energy and activity variables of light vehicles powered by internal combustion engines in real traffic, and as a result, to develop an instrument and an appropriate methodology for this purpose, and consequently to make a study of the different factors which influence the emissions and the fuel consumption of passenger cars in real traffic. The thesis begins developing a prospective study on other authors’ works about development of Portable Emission Measurement Systems (PEMS), problems associated with dynamic emission measurements and application studies on actual traffic using PEMS. As a result of this study, it was shown that a measuring system specifically designed for being on-board on a vehicle, which can measure in real time emission concentrations and exhaust flow, and at the same time to record motor vehicle and environment variables as the slope and atmospheric data, is needed; and the specifications and design parameters of the equipment are proposed. Although at the beginning of this research work there were already on the market some PEMS, in this Thesis a new system is researched, designed and built, called MIVECO – PEMS, in order to meet such measurements needs. Following that, there are presented, discussed and justify all technical solutions incorporated in the system, including the gas analysis subsystem, sampling and exhaust gas flowmeter subsystem, the subsystem for measurement of environment variables and of the vehicle activity and the set of auxiliary subsystems. The final design meets the needs and hypotheses proposed, and is validated in real-life use and chassis dynamometer testing and is also compared with other stationary and on-board systems. This thesis also presents all the research that has led to the methodology of processing the set of signals recorded in real time including signal timing, calculations and error propagation. The methodology to select and characterize of the routes and circuits, the driving patterns, and the vehicle preparation and calibration of the instruments and sensors are part of the legacy of this thesis. To demonstrate the measurement capabilities of the system and the type of results that can be obtained and that are useful for the scientific community and the environmental authorities, at the end of this Thesis is presented the results of several studies of endogenous and exogenous variables that affect the instantaneous and averaged emissions and consumption factors (g/km), as: driving style, road infrastructure, the level of traffic congestion, urban and extra-urban traffic, biofuels content, type of engine (diesel or spark ignition) etc. The main conclusions of this thesis are that it is possible to measure mass emissions and consumption of vehicle engines in actual use and that the results allow us to establish policies to reduce environmental impact and improve energy efficiency, but, to establish precise methodologies and to be very careful in the entire process of calibration, measurement and data post-treatment is necessary.

El problema del rozamiento en el análisis de estructuras de fábrica mediante modelos de sólidos rígidos

La evaluación de la seguridad de estructuras antiguas de fábrica es un problema abierto.El material es heterogéneo y anisótropo, el estado previo de tensiones difícil de conocer y las condiciones de contorno inciertas. A comienzos de los años 50 se demostró que el análisis límite era aplicable a este tipo de estructuras, considerándose desde entonces como una herramienta adecuada. En los casos en los que no se produce deslizamiento la aplicación de los teoremas del análisis límite estándar constituye una herramienta formidable por su simplicidad y robustez. No es necesario conocer el estado real de tensiones. Basta con encontrar cualquier solución de equilibrio, y que satisfaga las condiciones de límite del material, en la seguridad de que su carga será igual o inferior a la carga real de inicio de colapso. Además esta carga de inicio de colapso es única (teorema de la unicidad) y se puede obtener como el óptimo de uno cualquiera entre un par de programas matemáticos convexos duales. Sin embargo, cuando puedan existir mecanismos de inicio de colapso que impliquen deslizamientos, cualquier solución debe satisfacer tanto las restricciones estáticas como las cinemáticas, así como un tipo especial de restricciones disyuntivas que ligan las anteriores y que pueden plantearse como de complementariedad. En este último caso no está asegurada la existencia de una solución única, por lo que es necesaria la búsqueda de otros métodos para tratar la incertidumbre asociada a su multiplicidad. En los últimos años, la investigación se ha centrado en la búsqueda de un mínimo absoluto por debajo del cual el colapso sea imposible. Este método es fácil de plantear desde el punto de vista matemático, pero intratable computacionalmente, debido a las restricciones de complementariedad 0 y z 0 que no son ni convexas ni suaves. El problema de decisión resultante es de complejidad computacional No determinista Polinomial (NP)- completo y el problema de optimización global NP-difícil. A pesar de ello, obtener una solución (sin garantía de exito) es un problema asequible. La presente tesis propone resolver el problema mediante Programación Lineal Secuencial, aprovechando las especiales características de las restricciones de complementariedad, que escritas en forma bilineal son del tipo y z = 0; y 0; z 0 , y aprovechando que el error de complementariedad (en forma bilineal) es una función de penalización exacta. Pero cuando se trata de encontrar la peor solución, el problema de optimización global equivalente es intratable (NP-difícil). Además, en tanto no se demuestre la existencia de un principio de máximo o mínimo, existe la duda de que el esfuerzo empleado en aproximar este mínimo esté justificado. En el capítulo 5, se propone hallar la distribución de frecuencias del factor de carga, para todas las soluciones de inicio de colapso posibles, sobre un sencillo ejemplo. Para ello, se realiza un muestreo de soluciones mediante el método de Monte Carlo, utilizando como contraste un método exacto de computación de politopos. El objetivo final es plantear hasta que punto está justificada la busqueda del mínimo absoluto y proponer un método alternativo de evaluación de la seguridad basado en probabilidades. Las distribuciones de frecuencias, de los factores de carga correspondientes a las soluciones de inicio de colapso obtenidas para el caso estudiado, muestran que tanto el valor máximo como el mínimo de los factores de carga son muy infrecuentes, y tanto más, cuanto más perfecto y contínuo es el contacto. Los resultados obtenidos confirman el interés de desarrollar nuevos métodos probabilistas. En el capítulo 6, se propone un método de este tipo basado en la obtención de múltiples soluciones, desde puntos de partida aleatorios y calificando los resultados mediante la Estadística de Orden. El propósito es determinar la probabilidad de inicio de colapso para cada solución.El método se aplica (de acuerdo a la reducción de expectativas propuesta por la Optimización Ordinal) para obtener una solución que se encuentre en un porcentaje determinado de las peores. Finalmente, en el capítulo 7, se proponen métodos híbridos, incorporando metaheurísticas, para los casos en que la búsqueda del mínimo global esté justificada. Abstract Safety assessment of the historic masonry structures is an open problem. The material is heterogeneous and anisotropic, the previous state of stress is hard to know and the boundary conditions are uncertain. In the early 50's it was proven that limit analysis was applicable to this kind of structures, being considered a suitable tool since then. In cases where no slip occurs, the application of the standard limit analysis theorems constitutes an excellent tool due to its simplicity and robustness. It is enough find any equilibrium solution which satisfy the limit constraints of the material. As we are certain that this load will be equal to or less than the actual load of the onset of collapse, it is not necessary to know the actual stresses state. Furthermore this load for the onset of collapse is unique (uniqueness theorem), and it can be obtained as the optimal from any of two mathematical convex duals programs However, if the mechanisms of the onset of collapse involve sliding, any solution must satisfy both static and kinematic constraints, and also a special kind of disjunctive constraints linking the previous ones, which can be formulated as complementarity constraints. In the latter case, it is not guaranted the existence of a single solution, so it is necessary to look for other ways to treat the uncertainty associated with its multiplicity. In recent years, research has been focused on finding an absolute minimum below which collapse is impossible. This method is easy to set from a mathematical point of view, but computationally intractable. This is due to the complementarity constraints 0 y z 0 , which are neither convex nor smooth. The computational complexity of the resulting decision problem is "Not-deterministic Polynomialcomplete" (NP-complete), and the corresponding global optimization problem is NP-hard. However, obtaining a solution (success is not guaranteed) is an affordable problem. This thesis proposes solve that problem through Successive Linear Programming: taking advantage of the special characteristics of complementarity constraints, which written in bilinear form are y z = 0; y 0; z 0 ; and taking advantage of the fact that the complementarity error (bilinear form) is an exact penalty function. But when it comes to finding the worst solution, the (equivalent) global optimization problem is intractable (NP-hard). Furthermore, until a minimum or maximum principle is not demonstrated, it is questionable that the effort expended in approximating this minimum is justified. XIV In chapter 5, it is proposed find the frequency distribution of the load factor, for all possible solutions of the onset of collapse, on a simple example. For this purpose, a Monte Carlo sampling of solutions is performed using a contrast method "exact computation of polytopes". The ultimate goal is to determine to which extent the search of the global minimum is justified, and to propose an alternative approach to safety assessment based on probabilities. The frequency distributions for the case study show that both the maximum and the minimum load factors are very infrequent, especially when the contact gets more perfect and more continuous. The results indicates the interest of developing new probabilistic methods. In Chapter 6, is proposed a method based on multiple solutions obtained from random starting points, and qualifying the results through Order Statistics. The purpose is to determine the probability for each solution of the onset of collapse. The method is applied (according to expectations reduction given by the Ordinal Optimization) to obtain a solution that is in a certain percentage of the worst. Finally, in Chapter 7, hybrid methods incorporating metaheuristics are proposed for cases in which the search for the global minimum is justified.

Analysis of the Behaviour of Biofuel-Fired Gas Turbine Power Plants

The utilisation of biofuels in gas turbines is a promising alternative to fossil fuels for power generation. It would lead to significant reduction of CO2 emissions using an existing combustion technology, although significant changes seem to be needed and further technological development is necessary. The goal of this work is to perform energy and exergy analyses of the behaviour of gas turbines fired with biogas, ethanol and synthesis gas (bio-syngas), compared with natural gas. The global energy transformation process (i.e. from biomass to electricity) has also been studied. Furthermore, the potential reduction of CO2 emissions attained by the use of biofuels has been determined, considering the restrictions regarding biomass availability. Two different simulation tools have been used to accomplish the aims of this work. The results suggest a high interest and the technical viability of the use of Biomass Integrated Gasification Combined Cycle (BIGCC) systems for large scale power generation.

Coupling time-stepping numerical methods and standard aerodynamics codes for instability analysis of flows in complex geometries

The development of a global instability analysis code coupling a time-stepping approach, as applied to the solution of BiGlobal and TriGlobal instability analysis 1, 2 and finite-volume-based spatial discretization, as used in standard aerodynamics codes is presented. The key advantage of the time-stepping method over matrix-formulation approaches is that the former provides a solution to the computer-storage issues associated with the latter methodology. To-date both approaches are successfully in use to analyze instability in complex geometries, although their relative advantages have never been quantified. The ultimate goal of the present work is to address this issue in the context of spatial discretization schemes typically used in industry. The time-stepping approach of Chiba 3 has been implemented in conjunction with two direct numerical simulation algorithms, one based on the typically-used in this context high-order method and another based on low-order methods representative of those in common use in industry. The two codes have been validated with solutions of the BiGlobal EVP and it has been showed that small errors in the base flow do not have affect significantly the results. As a result, a three-dimensional compressible unsteady second-order code for global linear stability has been successfully developed based on finite-volume spatial discretization and time-stepping method with the ability to study complex geometries by means of unstructured and hybrid meshes

Multivariant non-failure analysis via standard abstract interpretation

Non-failure analysis aims at inferring that predicate calis in a program will never fail. This type of information has many applications in functional/logic programming. It is essential for determining lower bounds on the computational cost of calis, useful in the context of program parallelization, instrumental in partial evaluation and other program transformations, and has also been used in query optimization. In this paper, we re-cast the non-failure analysis proposed by Debray et al. as an abstract interpretation, which not only allows to investígate it from a standard and well understood theoretical framework, but has also several practical advantages. It allows us to incorpórate non-failure analysis into a standard, generic abstract interpretation engine. The analysis thus benefits from the fixpoint propagation algorithm, which leads to improved information propagation. Also, the analysis takes advantage of the multi-variance of the generic engine, so that it is now able to infer sepárate non-failure information for different cali patterns. Moreover, the implementation is simpler, and allows to perform non-failure and covering analyses alongside other analyses, such as those for modes and types, in the same framework. Finally, besides the precisión improvements and the additional simplicity, our implementation (in the Ciao/CiaoPP multiparadigm programming system) also shows better efRciency.

Global analysis of standard prolog programs

Abstract interpretation-based data-flow analysis of logic programs is, at this point, relatively well understood from the point of view of general frameworks and abstract domains. On the other hand, comparatively little attention has been given to the problems which arise when analysis of a full, practical dialect of the Prolog language is attempted, and only few solutions to these problems have been proposed to date. Existing proposals generally restrict in one way or another the classes of programs which can be analyzed. This paper attempts to fill this gap by considering a full dialect of Prolog, essentially the recent ISO standard, pointing out the problems that may arise in the analysis of such a dialect, and proposing a combination of known and novel solutions that together allow the correct analysis of arbitrary programs which use the full power of the language.

Analysis of noise temperature sensitivity for the design of a broadband thermal noise primary standard

A broadband primary standard for thermal noise measurements is presented and its thermal and electromagnetic behaviour is analysed by means of a novel hybrid analytical?numerical simulation methodology. The standard consists of a broadband termination connected to a 3.5mm coaxial airline partially immersed in liquid nitrogen and is designed in order to obtain a low reflectivity and a low uncertainty in the noise temperature. A detailed sensitivity analysis is made in order to highlight the critical characteristics that mostly affect the uncertainty in the noise temperature, and also to determine the manufacturing and operation tolerances for a proper performance in the range 10MHz to 26.5 GHz. Aspects such as the thermal bead design, the level of liquid nitrogen or the uncertainties associated with the temperatures, the physical properties of the materials in the standard and the simulation techniques are discussed.

Flujos de gases de efecto invernadero en suelos forestales y agroforestales del centro de la Península Ibérica=Greenhouse gas flows in forest and agroforestry soils in the center of the Iberian Peninsula

Debido a la complejidad de los procesos que controlan el intercambio de gases de carbono (C) y nitrógeno (N) entre el suelo y la atmósfera, en los sistemas forestales y agroforestales, son comprensibles las incógnitas existentes respecto a la estimación de los flujos de los gases de efecto invernadero (GEI) y la capacidad como reservorios de carbono de los suelos, bajo diferentes formas de uso y regímenes de alteración a escala regional y global. Esta escasez de información justifica la necesidad de caracterizar la dinámica de intercambio de GEI en los ecosistemas Mediterráneos, en especial en el contexto actual de cambio climático, y el incremento asociado de temperatura y periodos de sequía, alteración de los patrones de precipitación, y el riesgo de incendios forestales; cuyas consecuencias afectarán tanto a los compartimentos de C y de N del suelo como a la capacidad de secuestro de C de estos ecosistemas. Dentro de este contexto se enmarca la presente tesis doctoral cuyo objetivo ha sido cuantificar y caracterizar los flujos de dióxido de carbono (CO2), de oxido nitroso (N2O) y de metano (CH4), junto con los stocks de C y N, en suelos forestales de Quercus ilex, Quercus pyrenaica y Pinus sylvestris afectados por incendios forestales; así como el estudiar el efecto de la gestión y la cubierta arbórea en la respiración del suelo y los stocks de C y N en una dehesa situada en el centro de la Península Ibérica. De manera que los flujos de CO2, N2O y CH4; y los parámetros físico-químicos y biológicos del suelo fueron estudiados en los diferentes tratamientos y ecosistemas a lo largo del trabajo que se presenta. Los resultados obtenidos muestran la existencia de variaciones temporales y espaciales de la respiración del suelo dentro de una escala geográfica pequeña, controladas principalmente por la temperatura y la humedad del suelo; y por los contenidos de C y N del suelo en un bosque de Pinus sylvestris en la vertiente norte de la Sierra de Guadarrama , en España. El análisis de los efectos de los incendios forestales a largo plazo (6-8 años) revela que las pérdidas anuales de C a través de la respiración del suelo en las zonas quemadas de Quercus ilex, Quercus pyrenaica y Pinus sylvestris fueron 450 gCm-2yr-1, 790 gCm-2yr-1 y 1220 gCm-2yr-1, respectivamente; lo que representa una reducción del 43%, 22% y 11% en comparación con las zonas no quemadas de dichas especies, debido a la destrucción de la masa arbórea. El efecto del fuego también alteró los flujos N2O y CH4 del suelo, de una forma diferente en los distintos ecosistemas y estacionalidades estudiadas. De tal modo, que los suelos quemados mostraron una mayor oxidación del CH4 en las masas de Q. ilex, y una menor oxidación en las de P. sylvestris; además de una disminución de los flujos de N2O en Q. pyrenaica. Los incendios también afectaron los parámetros microclimáticos de los suelos forestales, observándose un incremento de la temperatura del suelo y una disminución de la humedad en los emplazamientos quemados que en los no quemados. Los cationes intercambiables, el pH, el cociente C/N, el contenido en raicillas y la biomasa microbiana también disminuyeron en las zonas quemadas. Aunque el C orgánico del suelo no se alteró de manera significativa, si lo hizo la calidad de la materia orgánica, disminuyendo el carbono lábil y aumentando las formas recalcitrantes lo que se tradujo en menor sensibilidad de la respiración del suelo a la temperatura (valores de Q10) en las zonas quemadas. Los resultados del estudio realizado en la Dehesa muestran que las actividades silvopastorales estudiadas afectaron levemente y de forma no constante a la respiración del suelo y las condiciones microclimáticas del suelo. Se observó una reducción 12% de la respiración del suelo por efecto del pastoreo no intensivo. Sin embargo, se observaron incrementos de 3Mg/ha en los stocks de C y de 0.3 Mg/ha en los stocks de N en los suelos pastoreados en comparación con los no pastoreados. Aunque, no se observó un claro efecto de la labranza sobre la respiración del suelo en nuestro experimento, sin embargo si se observó una disminución de 3.5 Mg/ha en las reservas de C y de 0.3 Mg/ ha en las de N en los suelos labrados comparados con los no labrados. La copa del arbolado influyó de forma positiva tanto en la respiración del suelo, como en los stocks de C y N de los suelos. La humedad del suelo jugó un papel relevante en la sensibilidad de la respiración a la temperatura del suelo. Nuestros resultados ponen de manifiesto la sensibilidad de la respiración del suelo a cambios en la humedad y los parámetros edáficos, y sugieren que la aplicación de modelos estándar para estimar la respiración del suelo en áreas geográficas pequeñas puede no ser adecuada a menos que otros factores sean considerados en combinación con la temperatura del suelo. Además, las diferentes respuestas de los flujos de gases de efecto invernadero a los cambios, años después de la ocurrencia de incendios forestales, destaca la necesidad de incluir estos cambios en las futuras investigaciones de la dinámica del carbono en los ecosistemas mediterráneos. Por otra parte, las respuestas divergentes en los valores de respiración del suelo y en los contenidos de C y N del suelo observados en la dehesa, además de la contribución de la copa de los árboles en los nutrientes del suelo ilustran la importancia de mantener la gestión tradicional aplicada en beneficio de la capacidad de almacenar C en la dehesa estudiada. La información obtenida en este trabajo pretende contribuir a la mejora del conocimiento de la dinámica y el balance de C en los sistemas mediterráneos, además de ayudar a predecir el impacto del cambio climático en el intercambio de C entre los ecosistemas forestales y agroforestales y la atmósfera. ABSTRACT Due to the complexity of the processes that control the exchange of carbon (C) and nitrogen (N) gasses between soils and the atmosphere in forest and agroforestry ecosystems, understandable uncertainties exist as regards the estimation of greenhouse gas (GHG) fluxes and the soil sink capacity at regional and global scale under different forms of land use and disturbance regimes. These uncertainties justify the need to characterize the exchange dynamics of GHG between the atmosphere and soils in Mediterranean terrestrial ecosystems, particularly in the current context of climate change and the associated increase in temperature, drought periods, heavy rainfall events, and increased risk of wildfires, which affect not only the C and N pools but also the soil C sink capacity of these ecosystems. Within this context, the aims of the present thesis were, firstly, to quantify and characterize the fluxes of carbon dioxide (CO2), nitrous oxide (N2O) and methane (CH4) as well as the C and N stocks in Quercus ilex, Quercus pyrenaica and Pinus sylvestris stands affected by wildfires, and secondly, to study the effects of Quercus ilex canopy and management on both soil respiration and C and N pools in dehesa systems in the center of Iberian Peninsula. Soil CO2, N2O and CH4 fluxes, and soil physical-chemical and biological parameters were studied under the different treatments and ecosystems considered in this study. The results showed seasonal and spatial variations in soil respiration within small geographic areas, mainly controlled by soil temperature and moisture in addition to soil carbon and nitrogen stocks in mixed pine–oak forest ecosystems on the north facing slopes of the Sierra de Guadarrama in Spain. The analysis of long term effects of wildfires (6–8 years) revealed that annual carbon losses through soil respiration from burned sites in Quercus ilex, Quercus pyrenaica and Pinus sylvestris stands were 450 gCm-2yr-1, 790 gCm-2yr-1 and 1220 gCm-2yr-1, respectively; with burned sites emitting 43%, 22% and 11% less in burned as opposed to non-burned sites due the loss of trees. Fire may alter both N2O and CH4 fluxes although the magnitude of such variation depends on the site, soil characteristics and seasonal climatic conditions. The burned sites showed higher CH4 oxidation in Q.ilex stands, and lower oxidation rates in P. sylvestris stands. A reduction in N2O fluxes in Q. pyrenaica stands was detected at burned sites along with changes in soil microclimate; higher soil temperature and lower soil moisture content. Exchangeable cations, the C/N ratio, pH, fine root and microbial biomass were also found to decrease at burned sites. Although the soil organic carbon was not significantly altered, the quality of the organic matter changed, displaying a decrease in labile carbon and a relative increase in refractory forms, leading to lower sensitivity of soil respiration to temperature (Q10 values) at burned sites. The results from the dehesa study show that light grazing and superficial tilling practices used in the studied dehesa system in Spain had a slight but non-consistent impact on soil respiration and soil microclimate over the study period. The reduction in soil respiration in the dehesa system due to the effects of grazing was around 12 %. However, increments of 3Mg/ha in C stocks and 0.3 Mg/ha in N stocks in grazed soils were observed. Although no clear effect of tilling on soil respiration was found, a decrease of 3.5 Mg/ha in C stocks and 0.3 Mg/ha in N stocks was detected for tilled soils. The presence of a tree canopy induced increases in soil respiration, soil C and N stocks, while soil moisture was found to play an important role in soil respiration temperature response. Our results suggest that the use of standard models to estimate soil respiration in small geographical areas may not be adequate unless other factors are considered in addition to soil temperature. Furthermore, the different responses of GHG flux to climatic shifts, many years after the occurrence of wildfire, highlight the need to include these shifts in C dynamics in future research undertaken in Mediterranean ecosystems. Furthermore, divergent responses in soil respiration and soil C and N stocks to grazing or tilling practices in Dehesa systems, and the influence of tree canopy on soil respiration and soil nutrient content, illustrate the importance of maintaining beneficial management practices. Moreover, the carbon sequestration capacity of the Dehesa system studied may be enhanced through improvements in the management applied. It is hoped that the information obtained through this research will contribute towards improving our understanding of the dynamics and balance of C in Mediterranean systems, and help predict the impact of climate change on the exchange of C between forest and agroforestry ecosystems and the atmosphere.

An Empirical Analysis of the Spanish Gas Price Structure

We can say without hesitation that in energy markets a throughout data analysis is crucial when designing sophisticated models that are able to capture most of the critical market drivers. In this study we will attempt to investigate into Spanish natural gas prices structure to improve understanding of the role they play in the determination of electricity prices and decide in the future about price modelling aspects. To further understand the potential for modelling, this study will focus on the nature and characteristics of the different gas price data available. The fact that the existing gas market in Spain does not incorporate enough liquidity of trade makes it even more critical to analyze in detail available gas price data information that in the end will provide relevant information to understand how electricity prices are affected by natural gas markets. In this sense representative Spanish gas prices are typically difficult to explore given the fact that there is not a transparent gas market yet and all the gas imported in the country is negotiated and purchased by private companies at confidential terms.

Multiresidue Analysis of Insecticides and Other Selected Environmental Contaminants in Poultry Manure by Gas Chromatography/Mass Spectrometry

An analytical method was developed for the simultaneous determination in poultry manure of 41 organic contaminants belonging to different chemical classes: pesticides, polycyclic aromatic hydrocarbons, polychlorinated biphenyls, and polybrominated diphenyl ethers. Poultry manure was extracted with a modified QuEChERS method, and the extracts were analyzed by isotope dilution GC/MS. Recovery of these contaminants from samples spiked at levels ranging from 25 to 100 ng/g was satisfactory for all the compounds. The developed procedure provided LODs from 0.8 to 9.6 ng/g. The analysis of poultry manure samples collected on different farms confirmed the presence of some of the studied contaminants. Pyrethroids and polycyclic aromatic hydrocarbons were the main contaminants detected.

Determination of selected pharmaceutical compounds in biosolids bysupported liquid extraction and gas chromatography?tandem massspectrometry

In this work, an analytical method was developed for the determination of pharmaceutical drugs inbiosolids. Samples were extracted with an acidic mixture of water and acetone (1:2, v/v) and supportedliquid extraction was used for the clean-up of extracts, eluting with ethyl acetate:methanol (90:10, v/v).The compounds were determined by gas chromatography?tandem mass spectrometry using matrix-match calibration after silylation to form their t-butyldimethylsilyl derivatives. This method presentsvarious advantages, such as a fairly simple operation for the analysis of complex matrices, the use ofinexpensive glassware and low solvent volumes. Satisfactory mean recoveries were obtained with thedeveloped method ranging from 70 to 120% with relative standard deviations (RSDs) ? 13%, and limitsof detection between 0.5 and 3.6 ng g?1. The method was then successfully applied to biosolids samplescollected in Madrid and Catalonia (Spain). Eleven of the sixteen target compounds were detected in thestudied samples, at levels up to 1.1 ?g g?1(salicylic acid). Ibuprofen, caffeine, paracetamol and fenofibratewere detected in all of the samples analyzed.