High Efficiency Envelope Amplifier based on a Ripple Cancellation Buck Converter. Design, Optimization and Integration in an EER RFPA

Durante los últimos años la tendencia en el sector de las telecomunicaciones ha sido un aumento y diversificación en la transmisión de voz, video y fundamentalmente de datos. Para conseguir alcanzar las tasas de transmisión requeridas, los nuevos estándares de comunicaciones requieren un mayor ancho de banda y tienen un mayor factor de pico, lo cual influye en el bajo rendimiento del amplificador de radiofrecuencia (RFPA). Otro factor que ha influido en el bajo rendimiento es el diseño del amplificador de radiofrecuencia. Tradicionalmente se han utilizado amplificadores lineales por su buen funcionamiento. Sin embargo, debido al elevado factor de pico de las señales transmitidas, el rendimiento de este tipo de amplificadores es bajo. El bajo rendimiento del sistema conlleva desventajas adicionales como el aumento del coste y del tamaño del sistema de refrigeración, como en el caso de una estación base, o como la reducción del tiempo de uso y un mayor calentamiento del equipo para sistemas portátiles alimentados con baterías. Debido a estos factores, se han desarrollado durante las últimas décadas varias soluciones para aumentar el rendimiento del RFPA como la técnica de Outphasing, combinadores de potencia o la técnica de Doherty. Estas soluciones mejoran las prestaciones del RFPA y en algún caso han sido ampliamente utilizados comercialmente como la técnica de Doherty, que alcanza rendimientos hasta del 50% para el sistema completo para anchos de banda de hasta 20MHz. Pese a las mejoras obtenidas con estas soluciones, los mayores rendimientos del sistema se obtienen para soluciones basadas en la modulación de la tensión de alimentación del amplificador de potencia como “Envelope Tracking” o “EER”. La técnica de seguimiento de envolvente o “Envelope Tracking” está basada en la modulación de la tensión de alimentación de un amplificador lineal de potencia para obtener una mejora en el rendimiento en el sistema comparado a una solución con una tensión de alimentación constante. Para la implementación de esta técnica se necesita una etapa adicional, el amplificador de envolvente, que añade complejidad al amplificador de radiofrecuencia. En un amplificador diseñado con esta técnica, se aumentan las pérdidas debido a la etapa adicional que supone el amplificador de envolvente pero a su vez disminuyen las pérdidas en el amplificador de potencia. Si el diseño se optimiza adecuadamente, puede conseguirse un aumento global en el rendimiento del sistema superior al conseguido con las técnicas mencionadas anteriormente. Esta técnica presenta ventajas en el diseño del amplificador de envolvente, ya que el ancho de banda requerido puede ser menor que el ancho de banda de la señal de envolvente si se optimiza adecuadamente el diseño. Adicionalmente, debido a que la sincronización entre la señal de envolvente y de fase no tiene que ser perfecta, el proceso de integración conlleva ciertas ventajas respecto a otras técnicas como EER. La técnica de eliminación y restauración de envolvente, llamada EER o técnica de Kahn está basada en modulación simultánea de la envolvente y la fase de la señal usando un amplificador de potencia conmutado, no lineal y que permite obtener un elevado rendimiento. Esta solución fue propuesta en el año 1952, pero no ha sido implementada con éxito durante muchos años debido a los exigentes requerimientos en cuanto a la sincronización entre fase y envolvente, a las técnicas de control y de corrección de los errores y no linealidades de cada una de las etapas así como de los equipos para poder implementar estas técnicas, que tienen unos requerimientos exigentes en capacidad de cálculo y procesamiento. Dentro del diseño de un RFPA, el amplificador de envolvente tiene una gran importancia debido a su influencia en el rendimiento y ancho de banda del sistema completo. Adicionalmente, la linealidad y la calidad de la señal de transmitida deben ser elevados para poder cumplir con los diferentes estándares de telecomunicaciones. Esta tesis se centra en el amplificador de envolvente y el objetivo principal es el desarrollo de soluciones que permitan el aumento del rendimiento total del sistema a la vez que satisfagan los requerimientos de ancho de banda, calidad de la señal transmitida y de linealidad. Debido al elevado rendimiento que potencialmente puede alcanzarse con la técnica de EER, esta técnica ha sido objeto de análisis y en el estado del arte pueden encontrarse numerosas referencias que analizan el diseño y proponen diversas implementaciones. En una clasificación de alto nivel, podemos agrupar las soluciones propuestas del amplificador de envolvente según estén compuestas de una o múltiples etapas. Las soluciones para el amplificador de envolvente en una configuración multietapa se basan en la combinación de un convertidor conmutado, de elevado rendimiento con un regulador lineal, de alto ancho de banda, en una combinación serie o paralelo. Estas soluciones, debido a la combinación de las características de ambas etapas, proporcionan un buen compromiso entre rendimiento y buen funcionamiento del amplificador de RF. Por otro lado, la complejidad del sistema aumenta debido al mayor número de componentes y de señales de control necesarias y el aumento de rendimiento que se consigue con estas soluciones es limitado. Una configuración en una etapa tiene las ventajas de una mayor simplicidad, pero debido al elevado ancho de banda necesario, la frecuencia de conmutación debe aumentarse en gran medida. Esto implicará un bajo rendimiento y un peor funcionamiento del amplificador de envolvente. En el estado del arte pueden encontrarse diversas soluciones para un amplificador de envolvente en una etapa, como aumentar la frecuencia de conmutación y realizar la implementación en un circuito integrado, que tendrá mejor funcionamiento a altas frecuencias o utilizar técnicas topológicas y/o filtros de orden elevado, que permiten una reducción de la frecuencia de conmutación. En esta tesis se propone de manera original el uso de la técnica de cancelación de rizado, aplicado al convertidor reductor síncrono, para reducir la frecuencia de conmutación comparado con diseño equivalente del convertidor reductor convencional. Adicionalmente se han desarrollado dos variantes topológicas basadas en esta solución para aumentar la robustez y las prestaciones de la misma. Otro punto de interés en el diseño de un RFPA es la dificultad de poder estimar la influencia de los parámetros de diseño del amplificador de envolvente en el amplificador final integrado. En esta tesis se ha abordado este problema y se ha desarrollado una herramienta de diseño que permite obtener las principales figuras de mérito del amplificador integrado para la técnica de EER a partir del diseño del amplificador de envolvente. Mediante el uso de esta herramienta pueden validarse el efecto del ancho de banda, el rizado de tensión de salida o las no linealidades del diseño del amplificador de envolvente para varias modulaciones digitales. Las principales contribuciones originales de esta tesis son las siguientes: La aplicación de la técnica de cancelación de rizado a un convertidor reductor síncrono para un amplificador de envolvente de alto rendimiento para un RFPA linealizado mediante la técnica de EER. Una reducción del 66% en la frecuencia de conmutación, comparado con el reductor convencional equivalente. Esta reducción se ha validado experimentalmente obteniéndose una mejora en el rendimiento de entre el 12.4% y el 16% para las especificaciones de este trabajo. La topología y el diseño del convertidor reductor con dos redes de cancelación de rizado en cascada para mejorar el funcionamiento y robustez de la solución con una red de cancelación. La combinación de un convertidor redactor multifase con la técnica de cancelación de rizado para obtener una topología que proporciona una reducción del cociente entre frecuencia de conmutación y ancho de banda de la señal. El proceso de optimización del control del amplificador de envolvente en lazo cerrado para mejorar el funcionamiento respecto a la solución en lazo abierto del convertidor reductor con red de cancelación de rizado. Una herramienta de simulación para optimizar el proceso de diseño del amplificador de envolvente mediante la estimación de las figuras de mérito del RFPA, implementado mediante EER, basada en el diseño del amplificador de envolvente. La integración y caracterización del amplificador de envolvente basado en un convertidor reductor con red de cancelación de rizado en el transmisor de radiofrecuencia completo consiguiendo un elevado rendimiento, entre 57% y 70.6% para potencias de salida de 14.4W y 40.7W respectivamente. Esta tesis se divide en seis capítulos. El primer capítulo aborda la introducción enfocada en la aplicación, los amplificadores de potencia de radiofrecuencia, así como los principales problemas, retos y soluciones existentes. En el capítulo dos se desarrolla el estado del arte de amplificadores de potencia de RF, describiéndose las principales técnicas de diseño, las causas de no linealidad y las técnicas de optimización. El capítulo tres está centrado en las soluciones propuestas para el amplificador de envolvente. El modo de control se ha abordado en este capítulo y se ha presentado una optimización del diseño en lazo cerrado para el convertidor reductor convencional y para el convertidor reductor con red de cancelación de rizado. El capítulo cuatro se centra en el proceso de diseño del amplificador de envolvente. Se ha desarrollado una herramienta de diseño para evaluar la influencia del amplificador de envolvente en las figuras de mérito del RFPA. En el capítulo cinco se presenta el proceso de integración realizado y las pruebas realizadas para las diversas modulaciones, así como la completa caracterización y análisis del amplificador de RF. El capítulo seis describe las principales conclusiones de la tesis y las líneas futuras. ABSTRACT The trend in the telecommunications sector during the last years follow a high increase in the transmission rate of voice, video and mainly in data. To achieve the required levels of data rates, the new modulation standards demand higher bandwidths and have a higher peak to average power ratio (PAPR). These specifications have a direct impact in the low efficiency of the RFPA. An additional factor for the low efficiency of the RFPA is in the power amplifier design. Traditionally, linear classes have been used for the implementation of the power amplifier as they comply with the technical requirements. However, they have a low efficiency, especially in the operating range of signals with a high PAPR. The low efficiency of the transmitter has additional disadvantages as an increase in the cost and size as the cooling system needs to be increased for a base station and a temperature increase and a lower use time for portable devices. Several solutions have been proposed in the state of the art to improve the efficiency of the transmitter as Outphasing, power combiners or Doherty technique. However, the highest potential of efficiency improvement can be obtained using a modulated power supply for the power amplifier, as in the Envelope Tracking and EER techniques. The Envelope Tracking technique is based on the modulation of the power supply of a linear power amplifier to improve the overall efficiency compared to a fixed voltage supply. In the implementation of this technique an additional stage is needed, the envelope amplifier, that will increase the complexity of the RFPA. However, the efficiency of the linear power amplifier will increase and, if designed properly, the RFPA efficiency will be improved. The advantages of this technique are that the envelope amplifier design does not require such a high bandwidth as the envelope signal and that in the integration process a perfect synchronization between envelope and phase is not required. The Envelope Elimination and Restoration (EER) technique, known also as Kahn’s technique, is based on the simultaneous modulation of envelope and phase using a high efficiency switched power amplifier. This solution has the highest potential in terms of the efficiency improvement but also has the most challenging specifications. This solution, proposed in 1952, has not been successfully implemented until the last two decades due to the high demanding requirements for each of the stages as well as for the highly demanding processing and computation capabilities needed. At the system level, a very precise synchronization is required between the envelope and phase paths to avoid a linearity decrease of the system. Several techniques are used to compensate the non-linear effects in amplitude and phase and to improve the rejection of the out of band noise as predistortion, feedback and feed-forward. In order to obtain a high bandwidth and efficient RFPA using either ET or EER, the envelope amplifier stage will have a critical importance. The requirements for this stage are very demanding in terms of bandwidth, linearity and quality of the transmitted signal. Additionally the efficiency should be as high as possible, as the envelope amplifier has a direct impact in the efficiency of the overall system. This thesis is focused on the envelope amplifier stage and the main objective will be the development of high efficiency envelope amplifier solutions that comply with the requirements of the RFPA application. The design and optimization of an envelope amplifier for a RFPA application is a highly referenced research topic, and many solutions that address the envelope amplifier and the RFPA design and optimization can be found in the state of the art. From a high level classification, multiple and single stage envelope amplifiers can be identified. Envelope amplifiers for EER based on multiple stage architecture combine a linear assisted stage and a switched-mode stage, either in a series or parallel configuration, to achieve a very high performance RFPA. However, the complexity of the system increases and the efficiency improvement is limited. A single-stage envelope amplifier has the advantage of a lower complexity but in order to achieve the required bandwidth the switching frequency has to be highly increased, and therefore the performance and the efficiency are degraded. Several techniques are used to overcome this limitation, as the design of integrated circuits that are capable of switching at very high rates or the use of topological solutions, high order filters or a combination of both to reduce the switching frequency requirements. In this thesis it is originally proposed the use of the ripple cancellation technique, applied to a synchronous buck converter, to reduce the switching frequency requirements compared to a conventional buck converter for an envelope amplifier application. Three original proposals for the envelope amplifier stage, based on the ripple cancellation technique, are presented and one of the solutions has been experimentally validated and integrated in the complete amplifier, showing a high total efficiency increase compared to other solutions of the state of the art. Additionally, the proposed envelope amplifier has been integrated in the complete RFPA achieving a high total efficiency. The design process optimization has also been analyzed in this thesis. Due to the different figures of merit between the envelope amplifier and the complete RFPA it is very difficult to obtain an optimized design for the envelope amplifier. To reduce the design uncertainties, a design tool has been developed to provide an estimation of the RFPA figures of merit based on the design of the envelope amplifier. The main contributions of this thesis are: The application of the ripple cancellation technique to a synchronous buck converter for an envelope amplifier application to achieve a high efficiency and high bandwidth EER RFPA. A 66% reduction of the switching frequency, validated experimentally, compared to the equivalent conventional buck converter. This reduction has been reflected in an improvement in the efficiency between 12.4% and 16%, validated for the specifications of this work. The synchronous buck converter with two cascaded ripple cancellation networks (RCNs) topology and design to improve the robustness and the performance of the envelope amplifier. The combination of a phase-shifted multi-phase buck converter with the ripple cancellation technique to improve the envelope amplifier switching frequency to signal bandwidth ratio. The optimization of the control loop of an envelope amplifier to improve the performance of the open loop design for the conventional and ripple cancellation buck converter. A simulation tool to optimize the envelope amplifier design process. Using the envelope amplifier design as the input data, the main figures of merit of the complete RFPA for an EER application are obtained for several digital modulations. The successful integration of the envelope amplifier based on a RCN buck converter in the complete RFPA obtaining a high efficiency integrated amplifier. The efficiency obtained is between 57% and 70.6% for an output power of 14.4W and 40.7W respectively. The main figures of merit for the different modulations have been characterized and analyzed. This thesis is organized in six chapters. In Chapter 1 is provided an introduction of the RFPA application, where the main problems, challenges and solutions are described. In Chapter 2 the technical background for radiofrequency power amplifiers (RF) is presented. The main techniques to implement an RFPA are described and analyzed. The state of the art techniques to improve performance of the RFPA are identified as well as the main sources of no-linearities for the RFPA. Chapter 3 is focused on the envelope amplifier stage. The three different solutions proposed originally in this thesis for the envelope amplifier are presented and analyzed. The control stage design is analyzed and an optimization is proposed both for the conventional and the RCN buck converter. Chapter 4 is focused in the design and optimization process of the envelope amplifier and a design tool to evaluate the envelope amplifier design impact in the RFPA is presented. Chapter 5 shows the integration process of the complete amplifier. Chapter 6 addresses the main conclusions of the thesis and the future work.

How do various maize crop models vary in their responses to climate change factors?

Comments This article is a U.S. government work, and is not subject to copyright in the United States. Abstract Potential consequences of climate change on crop production can be studied using mechanistic crop simulation models. While a broad variety of maize simulation models exist, it is not known whether different models diverge on grain yield responses to changes in climatic factors, or whether they agree in their general trends related to phenology, growth, and yield. With the goal of analyzing the sensitivity of simulated yields to changes in temperature and atmospheric carbon dioxide concentrations [CO2], we present the largest maize crop model intercomparison to date, including 23 different models. These models were evaluated for four locations representing a wide range of maize production conditions in the world: Lusignan (France), Ames (USA), Rio Verde (Brazil) and Morogoro (Tanzania). While individual models differed considerably in absolute yield simulation at the four sites, an ensemble of a minimum number of models was able to simulate absolute yields accurately at the four sites even with low data for calibration, thus suggesting that using an ensemble of models has merit. Temperature increase had strong negative influence on modeled yield response of roughly 0.5 Mg ha 1 per °C. Doubling [CO2] from 360 to 720 lmol mol 1 increased grain yield by 7.5% on average across models and the sites. That would therefore make temperature the main factor altering maize yields at the end of this century. Furthermore, there was a large uncertainty in the yield response to [CO2] among models. Model responses to temperature and [CO2] did not differ whether models were simulated with low calibration information or, simulated with high level of calibration information.

Dynamics of thermal ignition of spray flames in mixing layers

Conditions are identified under which analyses of laminar mixing layers can shed light on aspects of turbulent spray combustion. With this in mind, laminar spray-combustion models are formulated for both non-premixed and partially premixed systems. The laminar mixing layer separating a hot-air stream from a monodisperse spray carried by either an inert gas or air is investigated numerically and analytically in an effort to increase understanding of the ignition process leading to stabilization of high-speed spray combustion. The problem is formulated in an Eulerian framework, with the conservation equations written in the boundary-layer approximation and with a one-step Arrhenius model adopted for the chemistry description. The numerical integrations unveil two different types of ignition behaviour depending on the fuel availability in the reaction kernel, which in turn depends on the rates of droplet vaporization and fuel-vapour diffusion. When sufficient fuel is available near the hot boundary, as occurs when the thermochemical properties of heptane are employed for the fuel in the integrations, combustion is established through a precipitous temperature increase at a well-defined thermal-runaway location, a phenomenon that is amenable to a theoretical analysis based on activation-energy asymptotics, presented here, following earlier ideas developed in describing unsteady gaseous ignition in mixing layers. By way of contrast, when the amount of fuel vapour reaching the hot boundary is small, as is observed in the computations employing the thermochemical properties of methanol, the incipient chemical reaction gives rise to a slowly developing lean deflagration that consumes the available fuel as it propagates across the mixing layer towards the spray. The flame structure that develops downstream from the ignition point depends on the fuel considered and also on the spray carrier gas, with fuel sprays carried by air displaying either a lean deflagration bounding a region of distributed reaction or a distinct double-flame structure with a rich premixed flame on the spray side and a diffusion flame on the air side. Results are calculated for the distributions of mixture fraction and scalar dissipation rate across the mixing layer that reveal complexities that serve to identify differences between spray-flamelet and gaseous-flamelet problems.

Caracterización de parámetros petrofísicos relacionados con la capacidad de almacenamiento de CO2 en el acuífero salino profundo de Hontomín (Burgos)

La conciencia de la crisis de la modernidad -que comienza ya a finales del siglo XIX- ha cobrado más experiencia debido al conocimiento de los límites del desarrollo económico, ya que como parecía razonable pensar, también los recursos naturales son finitos. En 1972, el Club de Roma analizó las distintas opciones disponibles para conseguir armonizar el desarrollo sostenible y las limitaciones medioambientales. Fue en 1987 cuando la Comisión Mundial para el Medio Ambiente y el Desarrollo de la ONU definía por primera vez el concepto de desarrollo sostenible. Definición que posteriormente fue incorporada en todos los programas de la ONU y sirvió de eje, por ejemplo, a la Cumbre de la Tierra celebrada en Río de Janeiro en 1992. Parece evidente que satisfacer la demanda energética, fundamentalmente desde la Revolución Industrial en el s XIX, trajo consigo un creciente uso de los combustibles fósiles, con la consiguiente emisión de los gases de efecto invernadero (GEI) y el aumento de la temperatura global media terrestre. Esta temperatura se incrementó en los últimos cien años en una media de 0.74ºC. La mayor parte del incremento observado desde la mitad del siglo XX en esta temperatura media se debe, con una probabilidad de al menos el 90%, al aumento observado en los GEI antropogénicos, siendo uno de ellos el CO2 que proviene de la transformación del carbono de los combustibles fósiles durante su combustión. Ante el creciente uso de los combustibles fósiles, los proyectos CAC, proyectos de captura, transporte y almacenamiento, se presentan como una contribución al desarrollo sostenible ya que se trata de una tecnología que permite mitigar el cambio climático. Para valorar si la tecnología CAC es sostenible, habrá que comprobar si existe o no capacidad para almacenar el CO2 en una cantidad mayor a la de producción y durante el tiempo necesario que impone la evolución de la concentración de CO2 en la atmósfera para mantenerla por debajo de las 450ppmv (concentración de CO2 que propone el Panel Intergubernamental para el Cambio Climático). El desarrollo de los proyectos CAC completos pasa por la necesaria selección de adecuados almacenes de CO2 que sean capaces de soportar los efectos de las presiones de inyección, así como asegurar la capacidad de dichos almacenes y la estanqueidad del CO2 en los mismos. La caracterización geológica de un acuífero susceptible de ser almacén de CO2 debe conducir a determinar las propiedades que dicho almacén posee para asegurar un volumen adecuado de almacenamiento, una inyectabilidad del CO2 en el mismo a un ritmo adecuado y la estanqueidad del CO2 en dicho acuífero a largo plazo. El presente trabajo pretende estudiar los parámetros que tienen influencia en el cálculo de la capacidad del almacén, para lo que en primer lugar se ha desarrollado la tecnología necesaria para llevar a cabo la investigación mediante ensayos de laboratorio. Así, se ha desarrollado una patente, "ATAP, equipo para ensayos petrofísicos (P201231913)", con la que se ha llevado a cabo la parte experimental de este trabajo para la caracterización de los parámetros que tienen influencia en el cálculo de la capacidad del almacén. Una vez desarrollada la tecnología, se aborda el estudio de los distintos parámetros que tienen influencia en la capacidad del almacén realizando ensayos con ATAP. Estos ensayos definen el volumen del almacenamiento, llegándose a la conclusión de que en la determinación de este volumen, juegan un papel importante el alcance de los mecanismos trampa, físicos o químicos, del CO2 en el almacén. Ensayos que definen la capacidad del almacén de "aceptar" o "rechazar" el CO2 inyectado, la inyectabilidad, y por último, ensayos encaminados a determinar posibles fugas que se pueden dar a través de los pozos de inyección, definidos estos como caminos preferenciales de fugas en un almacén subterráneo de CO2. Queda de este modo caracterizada la estanqueidad del CO2 en el acuífero a largo plazo y su influencia obvia en la determinación de la capacidad del almacén. Unido al propósito de la estimación de la capacidad del almacén, se encuentra el propósito de asegurar la estanqueidad de dichos almacenes en el tiempo, y adelantarse a la evolución de la pluma de CO2 en el interior de dichos almacenes. Para cumplir este propósito, se ha desarrollado un modelo dinámico a escala de laboratorio, mediante el programa ECLIPSE 300, con el fin de establecer una metodología para el cálculo de la capacidad estimada del almacén, así como el estudio de la evolución de la pluma de CO2 dentro del acuífero a lo largo del tiempo, partiendo de los resultados obtenidos en los ensayos realizados en ATAP y con la modelización de la probeta de roca almacén empleada en dichos ensayos. Presentamos por tanto un trabajo que establece las bases metodológicas para el estudio de la influencia de distintos parámetros petrofísicos en el cálculo de la capacidad del almacén unidos al desarrollo tecnológico de ATAP y su utilización para la determinación de dichos parámetros aplicables a cada acuífero concreto de estudio. ABSTRACT The crisis of modernity –which begins at the end of 19th Century- has been more important due to the knowledge of the limits of economic development, since it appeared to be thought reasonable, the natural resources are finite. In 1972, The Club of Rome analyzed the different options available in order to harmonize the sustainability and the environment development. It was in 1987 when The Global Commission on The Environment and the Development of UN, defined for the first time the concept of Sustainable Development. This definition that was fully incorporated in all the UN programs and it was useful as an axis, for example, in La Cumbre de la Tierra summit in Río de Janeiro in 1992. It seems obvious to satisfy energetic demand, basically after The Industrial Revolution in 19th Century, which represented an increasing use of fossil fuels, therefore greenhouse gases emission and the increasing of global average temperature. This temperature increased in the last 100 years up to 0.74ºC. The major part of the temperature increase is due to the increase observed in Greenhouse gases with human origin, at least with 90% of probability. The most important gas is the CO2 because of its quantity. In the face of the increasing use of fossil fuels, the CCS projects, Carbon Capture and Storage projects, appear as a contribution of sustainable development since it is a technology for avoiding the climate change. In order to evaluate if CCS technology is sustainable, it will be necessary to prove if the capacity for CO2 storage is available or not in a quantity greater than the production one and during the time necessary to keep the CO2 concentration in the atmosphere lower than 450ppmv (concentration imposed by IPCC). The development of full CCS projects goes through the selection of good CO2 storages that are able to support the effects of pressure injection, and assure the capacity of such storages and the watertightness of CO2. The geological characterization of the aquifer that could be potential CO2 storage should lead to determine the properties that such storage has in order to assure the adequate storage volume, the CO2 injectivity in a good rate, and the watertightness of the CO2 in the long term. The present work aims to study the parameters that have influence on the calculation of storage capacity, and for that purpose the appropriate technology has been developed for carrying out the research by mean of laboratory tests. Thus, a patent has been developed, "ATAP, equipo para ensayos petrofísicos (P201231913)", that has been used for developing the experimental part of this work. Once the technology has been developed, the study of different parameters, that have influence on the capacity of the storage, has been addressed developing different tests in ATAP. These tests define the storage volume which is related to the scope of different CO2 trap mechanisms, physical or chemical, in the storage. Tests that define the capacity of the storage to “accept” or “reject” the injected CO2, the injectivity, and tests led to determine possible leakages through injection wells. In this way we could talk about the watertightness in the aquifer in the long term and its influence on the storage capacity estimation. Together with the purpose of the storage capacity estimation, is the purpose of assuring the watertightness of such storages in the long term and anticipating the evolution of CO2 plume inside such aquifers. In order to fulfill this purpose, a dynamic model has been developed with ECLIPSE 300, for stablishing the methodology for the calculation of storage capacity estimation and the evolution of the CO2 plume, starting out with the tests carried out in ATAP. We present this work that establishes the methodology bases for the study of the influence of different petrophysics parameters in the calculation of the capacity of the storage together with the technological development of ATAP and its utilization for the determination of such parameters applicable to each aquifer.

Metodología de integración de actividades de adaptación al cambio climático en proyectos de desarrollo rural

Hoy en día, ya no se puede pasar por alto la necesidad de una agricultura climáticamente más inteligente para los 500 millones de pequeños agricultores del mundo (Wheeler, 2013). Estos representan aproximadamente el 60 % de la agricultura mundial y proporcionan hasta el 80 % de los alimentos en los países en vías de desarrollo, los pequeños agricultores gestionan vastas extensiones de tierra y lamentablemente incluyen los grupos con mayor proporción de personas en estado de inseguridad alimentaria. El cambio climático está transformando el contexto para la agricultura en pequeña escala. Durante siglos, los pequeños agricultores desarrollaron la capacidad de adaptarse a los cambios ambientales y la variabilidad del clima, pero la velocidad y la intensidad del cambio climático está superando su capacidad de respuesta. Si no se cambia la manera que tenemos de lidiar con el cambio climático, tanto en acciones locales como globales, es muy probable que las personas rurales de entornos vulnerables tengan que adaptarse a un calentamiento global promedio de 4 °C por encima de los niveles preindustriales para el año 2100. Esta alza de las temperaturas aumentará aún más la incertidumbre y provocará desastres naturales como las sequías, la erosión del suelo, la pérdida de biodiversidad y la escasez agua sean mucho más frecuentes. Uno de los factores más importantes para los pequeños agricultores es que ya no pueden depender de los promedios históricos, por lo que es más difícil para ellos para planificar y gestionar la producción debido a los cambios en los patrones climáticos. Algunos de los principales cultivos de cereales (trigo, arroz, maíz, etc.) han alcanzado su umbral de tolerancia al calor y un aumento de la temperatura en torno a 1,5-2 °C podría ser muy perjudicial. Estos efectos a corto plazo podrían ser agravados por otros a medio y largo plazo, los que se refieren al impacto socioeconómico en términos de oportunidades y estabilidad política. El cambio climático está haciendo que el desarrollo de la pequeña agricultura resulte mucho más caro. A nivel de proyectos, los programas resistentes al clima tienen, normalmente, unos costos iniciales más altos, tanto de diseño como de implementación. Por ejemplo, es necesario incluir gastos adicionales en infraestructura, operación y mantenimiento; desarrollo de nuevas capacidades y el intercambio de conocimientos en torno al cambio climático. También se necesita mayor inversión para fortalecer las instituciones frente a los nuevos retos que propone el cambio climático, o generar información que pueda ser de escala reducida y con enfoques que beneficien a la comunidad, el cambio climático es global pero los efectos son locales. Es, por tanto, el momento de redefinir la relación entre agricultura y medio ambiente, ya que se hace cada vez más necesario buscar mejores y más eficientes maneras para responder al cambio climático. Es importante señalar que la respuesta al cambio climático no significa reinventar todo lo que se ha aprendido sobre el desarrollo, significa aplicar un esfuerzo renovado para hacer frente a los cambios en el trabajo de cooperación al desarrollo de una manera más sistemática y más amplia. Una respuesta coherente al cambio climático requiere que la comunidad internacional reconozca la necesidad de aumentar el apoyo financiero para la adaptación así como un mayor énfasis en proporcionar soluciones diseñadas para aumentar la resiliencia1 de los pequeños agricultores a las crisis relacionadas con el clima. Con el fin de responder a algunos de los desafíos mencionados anteriormente, esta investigación pretende contribuir a fortalecer las capacidades de los pequeños productores, aquellos que actualmente están la primera línea frente a los desafíos del cambio climático, promoviendo un desarrollo que tenga un impacto positivo en sus medios de vida. La tesis se compone de cuatro capítulos. El primero define y analiza el marco teórico de las interacciones entre el cambio climático y el impacto en los proyectos de desarrollo rural, especialmente los que tienen por objetivo mejorar la seguridad alimentaria de los pequeños productores. En ese mismo capítulo, se presenta una revisión global de la financiación climática, incluyendo la necesidad de asignar suficientes recursos para la adaptación. Con el fin de lograr una mayor eficacia e impacto en los proyectos de desarrollo, la investigación desarrolla una metodología para integrar actividades de adaptación al cambio climático, presentada en el segundo capítulo. Esta metodología fue implementada y validada durante el periodo 2012-14, trabajando directamente con diferentes equipos gubernamentales en diez proyectos del Fondo Internacional de Desarrollo Agrícola ). El tercero presenta, de manera detallada, la aplicación de la metodología a los estudios de caso de Bolivia y Nicaragua, así como un resumen de las principales conclusiones en la aplicación de los ocho países restantes. Finalmente, en el último capítulo se presentan las conclusiones y un esbozo de futuras líneas de investigación. Actualmente, el tema de la sostenibilidad ambiental y el cambio climático está ganando terreno en la agenda de desarrollo. Es por ello que se alumbra esta investigación, para que a través de los resultados obtenidos y la implementación de la metodología propuesta, sirva como herramienta estratégica para la planificación y la gestión operativa a la hora de integrar iniciativas de adaptación en los proyectos de desarrollo rural. ABSTRACT The need for climate-smart agriculture for the world’s 500 million smallholder farms cannot be overlooked: they account for 60 per cent of global agriculture, provide up to 80 per cent of food in developing countries, manage vast areas of land and make up the largest share of the developing world’s undernourished. Climate change is transforming the context for smallholder agriculture. Over centuries smallholders have developed the capacity to adapt to environmental change and climate variability, but the speed and intensity of climate change is outpacing the speed of historically autonomous actions. In the absence of a profound step-change in local and global action on climate change, it is Increasingly likely that poor rural people would need to contend with an average global warming of 4 degrees above pre-industrial levels by 2100, if not sooner. Such substantial climatic change will further increase uncertainty and exacerbate weather –related disasters, droughts, biodiversity loss, and land and water scarcity. Perhaps most significantly for smallholder farmers, they can no longer rely on historical averages, making it harder for them to plan and manage production when planting seasons and weather patterns are shifting. The major cereal crops (wheat, rice, maize, etc.) are at their heat tolerance threshold and with a 1.5-2°C temperature increase could collapse. These “first-round” effects will be compounded by second-round socio-economic impacts in terms of economic opportunities and political stability. Climate change is making the development of smallholder agriculture more expensive. At project level, climate-resilient programmes typically have higher up-front design and implementation costs – e.g. infrastructure costs and initially increased asset management, operation and maintenance, more capacity-building and knowledge sharing, strengthening institutions, greater project development costs (downscaled data generation and community-based approaches), and greater costs from enhancing cross sectorial and stakeholders collaboration. Consequently it’s time to redefine the relationship between agriculture and environment as we need to look better and more efficient ways to respond to climate change. It is important to note that responding to climate change does not mean to throwing out or reinventing everything that has been learnt about development. It means a renewed effort to tackle wider and well-known development changes in a more systematic way. A coherent response to climate change requires acknowledge of the need to increase the financial support for adaptation and a continued emphasis on provided solutions designed to increase the resilience of smallholders and poor communities to shocks, which are weather related. In order to respond to some of the challenges mentioned before, this research aims to contribute to strengthen the capacities of the smallholders and to promote a development that will positively impact in the rural livelihoods of the most vulnerable smallholders farmers; those who currently are in the first line facing the challenges of climate change. The thesis has four chapters. Chapter one describes and analyses the theoretical framework of the interactions between climate change and the impact on rural development projects, especially those aimed at improving the food security of smallholders producers. In this chapter a comprehensive review of climate financing is presented, including the need to allocate sufficient resources for adaptation. In order to achieve greater effectiveness and impact on development projects, the research develops in the second chapter a methodology to integrate adaptation activities for climate change. This methodology was implemented and validated during the 2012-14 period, working directly with various government teams in ten projects of the International Fund for Agricultural Development (IFAD). The third chapter presents in detail the application of the methodology to the case studies of Bolivia and Nicaragua, as well as a summary of the main conclusions of its implementation in the remaining eight countries. The final chapter exposes the main conclusions and future research topics. At a time when environmental sustainability and climate change issues are gaining more attention, the research and obtained results through the implementation of the model methodology proposed, can be considered a strategic tool for planning and operational management to integrate adaptation initiatives in rural development projects. The use of the proposed methodology will boost incentives to scale up climate resilience programmes and integrate adaptation to climate change into wider smallholder development programmes.

Propuesta metodológica de evaluación de la pobreza energética en España: indicadores para la rehabilitación de viviendas

La pobreza energética es un fenómeno que afecta a un número cada vez mayor de hogares de la Unión Europea. Es por ello que resulta urgente el desarrollo de definiciones de pobreza energética adaptadas a las condiciones regionales que recojan no sólo los distintos niveles de renta de los hogares de cada país, sino también las significativas diferencias constructivas y climáticas existentes entre el norte y el sur, de modo que incorporen los problemas de sobrecalentamiento y las necesidades de climatización que además se verán exacerbadas por el incremento de temperaturas provocado por el cambio climático. En este contexto, se plantea esta investigación cuyo objetivo fundamental es desarrollar un método de evaluación de la pobreza energética de los hogares en el contexto español que incorpore las particularidades climáticas, edificatorias y socioeconómicas del país. Este método debe servir como herramienta en la identificación de los hogares que se encuentran en situación de pobreza energética, así como el grado de necesidad de los mismos. Además de esto, y dado que la calidad de las viviendas es, junto con el nivel de renta y el precio de la energía, una de las causas principales de la pobreza energética, el método constituye una ayuda en la toma de decisiones de cara al desarrollo de políticas y actuaciones de rehabilitación energética de viviendas. La propuesta de un nuevo método de evaluación de la pobreza energética en España surge de las limitaciones encontradas en las metodologías actuales para detectar correctamente los hogares en situación de pobreza energética, debido a las particularidades de las distintas regiones del país. Así, a partir de las carencias detectadas, se propone un método basado en el enfoque de ingresos y gastos, en el que además se incorpora el parámetro de la pobreza monetaria. En este método también se contempla el concepto de vulnerabilidad frente a la pobreza energética, de modo que, no sólo clasifica a los hogares como pobres energéticos o no, sino que valora el potencial de un hogar de caer en una situación de pobreza energética. El método permite, por tanto, la clasificación de los hogares en distintos grupos en función de su situación de pobreza energética y/o monetaria teniendo también en cuenta su grado de vulnerabilidad frente a las mismas. Gracias a esta división por grupos, es posible, en primer lugar, detectar aquellos hogares sobre los que resulta prioritario intervenir, así como el tipo de intervención que se debe acometer. Además de esto, la detección de grupos vulnerables permite prever posibles futuras situaciones de pobreza energética y por tanto tomar las medidas necesarias para que éstas no se produzcan. El desarrollo del método se ha realizado a través de una serie de ajustes, los cuales han ido modificándolo mediante la aplicación del mismo a distintas escalas y muestras de datos. A lo largo de la investigación que ha permitido la definición de este método, se ha establecido la incidencia de la pobreza energética en Castilla y León, la Comunidad de Madrid y Andalucía, las tres comunidades autónomas seleccionadas como casos de estudio, pudiendo delimitar aquellos hogares que se encuentran en situación de pobreza energética. También se ha establecido la relación entre la pobreza energética y la pobreza monetaria y las sinergias que se producen entre éstas y el parque de viviendas en el que habitan los hogares más desfavorecidos, el cual también se ha caracterizado y definido. Por último, mediante la selección de una muestra representativa de este parque de viviendas, se han establecido, mediante la utilización de criterios de bienestar adaptativo, las condiciones mínimas de habitabilidad que este parque debe proporcionar y las necesidades energéticas y de gasto asociados a este parque. ABSTRACT Fuel poverty affects an increasing number of households in the European Union. It is urgent the development of fuel poverty definitions adapted to regional conditions that gather not only different income levels but important construction and climatic differences between Northern and Southern countries. Furthermore, these definitions must include overheating problems and subsequent cooling needs that will likely be exacerbated by temperature increase due to climate change. In this context, the present research is aimed at developing a method for evaluating fuel poverty within the Spanish context that gathers climatic, building and socioeconomic particularities of the country. This method must constitute a useful tool for the identification of the fuel poor as well as the degree of the required need. Given that dwelling energy quality is, with income levels and energy prices, one of the main causes of fuel poverty, the method poses an aid in the decision making processes related to policy development and dwelling energy retrofitting actions. The proposal of a new method for evaluating fuel poverty in Spain relies on the limitations detected in existing methods in order to adequate delimit the fuel poor, due to the existing differences across Spanish regions. Grounded on these shortfalls, a new method is proposed; based on the income and expenditure approach, it also incorporates the parameter of monetary poverty. The concept of vulnerability towards fuel poverty is reflected too, so households can be classified as being fuel poor or not as well as their potential to fall under fuel poverty. The method allows the classification of households into different groups according to their situation regarding fuel or monetary poverty, also taking into account their vulnerability degree towards them. This division by groups enables establishing retrofitting intervention priorities of some groups over the others as well as the most appropriate type of intervention. Besides that, the detection of vulnerable groups helps to foresee possible situations of fuel poverty in the future and thus to take actions to prevent them. The development of the method was carried out through several adjustments. The modification of the method through these adjustments was the result of the analysis of different scale and source data. Along with the development of the method, the incidence of fuel poverty was established for the three Autonomous Regions selected as study cases; Castilla y León, the Autonomous Region of Madrid and Andalucía. The relation between fuel and monetary poverty was determined as well as the interactions amongst these two parameters and the housing stock where the fuel poor live in. This housing stock was characterized and a representative sample of it was selected. Minimal thermal habitability conditions that should be guaranteed for the fuel poor were determined based on adaptive thermal comfort criteria. Accordingly, energy needs and expenditure of this housing stock derived from these minimum requirements were appraised.

Strategies to unblock the n-GaAs surface when electrodepositing Bi from acidic solutions

Bismuth ultra-thin films grown on n-GaAs electrodes via electrodeposition are porous due to a blockade of the electrode surface caused by adsorbed hydrogen when using acidic electrolytes. In this study, we discuss the existence of two sources of hydrogen adsorption and we propose different routes to unblock the n-GaAs surface in order to improve Bi films compactness. Firstly, we demonstrate that increasing the electrolyte temperature provides compact yet polycrystalline Bi films. Cyclic voltammetry scans indicate that this low crystal quality might be a result of the incorporation of Bi hydroxides within the Bi film as a result of the temperature increase. Secondly, we have illuminated the semiconductor surface to take advantage of photogenerated holes. These photocarriers oxidize the adsorbed hydrogen unblocking the surface, but also create pits at the substrate surface that degrade the Bi/GaAs interface and prevent an epitaxial growth. Finally, we show that performing a cyclic voltammetry scan before electrodeposition enables the growth of compact Bi ultra-thin films of high crystallinity on semiconductor substrates with a doping level low enough to perform transport measurements.

Climate simulation for 125 kyr BP with a coupled ocean-atmosphere general circulation model

The ECHAM-1 T21/LSG coupled ocean-atmosphere general circulation model (GCM) is used to simulate climatic conditions at the last interglacial maximum (Eemian. 125 kyr BP). The results reflect thc expected surface temperature changes (with respect to the control run) due to the amplification (reduction) of the seasonal cycle of insolation in the Northern (Southern) Hemisphere. A number of simulated features agree with previous results from atmospheric GCM simulations e.g. intensified summer southwest monsoons) except in the Northern Hemisphere poleward of 30 degrees N. where dynamical feedback, in the North Atlantic and North Pacific increase zonal temperatures about 1 degrees C above what would be predicted from simple energy balance considerations. As this is the same area where most of the terrestrial geological data originate, this result suggests that previous estimates of Eemian global average temperature might have been biased by sample distribution. This conclusion is supported by the fact that the estimated global temperature increase of only 0.3 degrees C greater than the control run ha, been previously shown to be consistent a with CLIMAP sea surface temperature estimates. Although the Northern Hemisphere summer monsoon is intensified. globally averaged precipitation over land is within about 1% of the present, contravening some geological inferences bur not the deep-sea delta(13)C estimates of terrestrial carbon storage changes. Winter circulation changes in the northern Arabian Sea. driven by strong cooling on land, are as large as summer circulation changes that are the usual focus of interest, suggesting that interpreting variations in the Arabian Sea. sedimentary record solely in terms of the summer monsoon response could sometimes lead to errors. A small monsoonal response over northern South America suggests that interglacial paleotrends in this region were not just due to El Nino variations.

Economic and climate change pressures on biodiversity in southern Mediterranean coastal areas. MEDPRO Technical Report No. 24/February 2013

This paper establishes and measures key biodiversity and ecosystem health indicators and the number of world heritage sites in coastal areas at global level. It then estimates – econometrically – the indicators’ influence on the provision of tourism values through the marine ecosystem function as a harbour of biodiversity, and as a provider of amenity values and marine cultural identity. The report then focuses on the MEDPRO region, providing some estimates of the potential impact of climate change on these services for a given temperature increase scenario. Finally, the effect on ecosystemrelated tourism is computed for the four MEDPRO social economic scenarios. The analysis is enriched by some quantification of the potential costs of adaptation.

Growth and carbon metabolism of the seaweed Fucus vesiculosus in the western Baltic Sea ("Kiel Outdoor Benthocosms")

Warming and acidification of the oceans as a consequence of increasing CO2-concentrations occur at large scales. Numerous studies have shown the impact of single stressors on individual species. However, studies on the combined effect of multiple stressors on a multi-species assemblage, which is ecologically much more realistic and relevant, are still scarce. Therefore, we orthogonally crossed the two factors warming and acidification in mesocosm experiments and studied their single and combined impact on the brown alga Fucus vesiculosus associated with its natural community (epiphytes and mesograzers) in the Baltic Sea in all seasons (from April 2013 to April 2014). We superimposed our treatment factors onto the natural fluctuations of all environmental variables present in the Benthocosms in so-called delta-treatments. Thereby we compared the physiological responses of F. vesiculosus (growth and metabolites) to the single and combined effects of natural Kiel Fjord temperatures and pCO2 conditions with a 5 °C temperature increase and/or pCO2 increase treatment (1100 ppm in the headspace above the mesocosms). Responses were also related to the factor photoperiod which changes over the course of the year. Our results demonstrate complex seasonal pattern. Elevated pCO2 positively affected growth of F. vesiculosus alone and/or interactively with warming. The response direction (additive, synergistic or antagonistic), however, depended on season and daylength. The effects were most obvious when plants were actively growing during spring and early summer. Our study revealed for the first time that it is crucial to always consider the impact of variable environmental conditions throughout all seasons. In summary, our study indicates that in future F. vesiculosus will be more affected by detrimental summer heat-waves than by ocean acidification although the latter consequently enhances growth throughout the year. The mainly negative influence of rising temperatures on the physiology of this keystone macroalga may alter and/or hamper its ecological functions in the shallow coastal ecosystem of the Baltic Sea.

Paleotemperature reconstructions of the Atlantic Sector of the Southern Ocean

Diatom assemblages from ODP Leg 177 sites 1093, 1094 and core PS2089-2, from the present Antarctic sea ice free zone and close to the Polar Front, were analyzed in order to reconstruct the climate development around the Mid-Brunhes Event 400 000 yr ago, as reflected by summer sea surface temperature (SSST) and sea ice distribution. Dense sample spacing allows a mean temporal resolution during Marine Isotope Stage (MIS) 11 (423-362 ka) of 300-400 yr. SSST values were estimated from diatom assemblages using a transfer function technique. The distribution pattern of sea ice diatoms indicates that the present-day ice free Antarctic Zone was seasonally covered by sea ice during the cold MIS 12 and MIS 10. These glacial periods are characterized by sea ice fluctuations with a periodicity of 3 and 1.85 kyr, suggesting the occurrence of Dansgaard-Oeschger-style millennial-scale oscillations in the Atlantic sector of the Southern Ocean during the glacial stages MIS 12 and MIS 10. Termination V (MIS 12/11) is characterized by a distinct temperature increase of 4-6°C, intersected especially at the southern site 1094 and core PS2089-2 by two distinct cooling events reminiscent of the Younger Dryas, which are associated with a northward shift of the winter sea ice edge in the Antarctic Zone. The SSST record is characterized by distinct temperature intervals bounded by stepwise, rapid changes. Maximum temperatures were reached during Termination V and the early MIS 11, exceeding modern values by 2°C over a period of 8 kyr. This pattern indicates a very early response of the Southern Ocean to global climate on Milankovitch-driven climate variability. The SSST optimum is marked by millennial-scale temperature oscillations with an amplitude of ca. 1°C and periodicities of ca. 1.85 and 1.47 kyr, probably reflecting changes in the ocean circulation system. The SSSTs during the MIS 11 temperature optimum do not exceed values obtained from other interglacial optima such as the early periods of MIS 5 or MIS 1 from the Antarctic Zone. However, the total duration of the warmest period was distinctly longer than observed from other interglacials. The comparison of the South Atlantic climate record with a high-resolution record from ODP Leg 162, site 980from the North Atlantic shows a strong conformity in the climate development during the studied time interval.

Timing and chemistry of fluid-flow events in the Lawn Hill Platform, Northern Australia

Mudrocks and carbonates of the Isa superbasin in the Lawn Hill platform in northern Australia host major base metal sulfide mineralization, including the giant strata-bound Century Zn-Pb deposit. Mineral paragenesis, stable isotope, and K-Ar dating studies demonstrate that long-lived structures such as the Termite Range fault acted as hot fluid conduits several times during the Paleoproterozoic and Mesoproterozoic in response to major tectonic events. Illite and chlorite crystallinity studies suggest the southern part of the platform has experienced higher temperatures (up to 300 degrees C) than similar stratigraphic horizons in the north. The irregular downhole variation of illite crystallinity values provides further information oil the thermal regime in the basin and shows that clay formation was controlled not only by temperature increase with depth but also by high water/rock ratios along relatively permeable zones. K-Ar dating of illite, in combination with other data, may indicate three major thermal events in the central and northern Lawn Hill platform Lit 1500, 1440 to 1400, and 1250 to 1150 Ma. This study did not detect the earlier Century base metal mineralizing event at 1575 Ma. 1500 Ma ages are recorded only in the south and correspond to the age of the Late Isan orogeny and deposition of the Lower Roper superbasin. They may reflect exhumation of a provenance region. The 1440 to 1300 Ma ages are related to fault reactivation and a thermal pulse at similar to 1440 to 1400 Ma possibly accompanied by fluid flow, with subsequent enhanced cooling possibly due to thermal relaxation or further crustal exhumation. The youngest thermal and/or fluid-flow event at 1250 to 1150 Ma is recorded mainly to the cast of the Tern-lite Range fault and may be related to the assembly of the Rodinian supercontinent. Fluids in equilibrium with illite that formed over a range of temperatures, at different times in different parts of the platform. have relatively uniform oxygen isotope compositions and more variable hydrogen isotope compositions (delta O-18 = 3.5-9.7 parts per thousand V-SMOW; delta D = -94 to -36 parts per thousand V-SMOW). The extent of the 180 enrichment and the variably depleted hydrogen isotope compositions suggest the illite interacted with deep-basin hypersaline brines that were composed of evaporated seawater and/or highly evolved meteoric water. Siderite is the most abundant iron-rich gangue phase in the Century Zn-Pb deposit, which is surrounded by all extensive ferroan carbonate alteration halo. Modeling suggests that the ore siderite formed at temperatures of 120 degrees to 150 degrees C, whereas siderite and ankerite in the alteration halo formed at temperatures of 150 degrees to 180 degrees C. The calculated isotopic compositions of the fluids are consistent with O-18-rich basinal brines and mixed inorganic and organic carbon Sources (6180 = 3-10 parts per thousand V-SMOW, delta C-13 = -7 to -3 parts per thousand V-PDB). in the northeast Lawn Hill platform carbonate-rich rocks preserve marine to early diagenetic carbon and oxygen isotope compositions, whereas ferroan carbonate cements in siltstones and shales in the Desert Creek borehole are O-18 and C-13 depleted relative to the sedimentary carbonates. The good agreement between temperature estimates from illite crystallinity and organic reflectance (160 degrees-270 degrees C) and inverse correlation with carbonate delta O-18 values indicates that organic maturation and carbonate precipitation in the northeast Lawn Hill platform resulted from interaction with the 1250 to 1150 Ma fluids. The calculated isotopic compositions of the fluid are consistent with evolved basinal brine (delta O-18 = 5.1-9.4 parts per thousand V-SMOW; delta C-13 = -13.2 to -3.7 parts per thousand V-PDB) that contained a variable organic carbon component from the oxidation and/or hydrolysis of organic matter in the host sequence. The occurrence of extensive O-18- and C-13-depleted ankerite and siderite alteration in Desert Creek is related to the high temperature of the 1250 to 1150 Ma fluid-flow event in the northeast Lawn Hill platform, in contrast to the lower temperature fluids associated with the earlier Century Zn-Pb deposit in the central Lawn Hill platform.

Hot-spots during the calcination of MCM-41:a SAXS comparative analysis of a soft mesophase

The phenomenon of microscopic hot-spots, during the calcination of MCM-41, was investigated by quantifying the magnitude of the temperature increase during the calcination of a soft MCM-41 mesophase using a SAXS comparative study. This was performed by thermally treating a soft material that was detemplated via Fenton chemistry followed by equilibrating and drying in a low-surface-tension solvent (n-butanol or N,N-dimethylformamide); these samples have limited structural shrinkage. The resulting samples were thermally treated at increasing temperatures, and the structural shrinkage was compared with that of the directly calcined material. By comparing the structural shrinkage, it was found that the microscopic temperature increase would fall between 190 and 250 C, as deduced from N,N-dimethyl-formamide and n-butanol. The order of magnitude of the temperature increase appears to be consistent with the well-known glow effect. It is, however, substantially higher than the experimentally determined macroscopic temperature increase. Several aspects are discussed to interpret this difference. © 2013 Elsevier B.V.

Physiological energetics of the thick shell mussel Mytilus coruscus exposed to seawater acidification and thermal stress

Anthropogenic CO2 emissions have caused seawater temperature elevation and ocean acidification. In view of both phenomena are occurring simultaneously, their combined effects on marine species must be experimentally evaluated. The purpose of this study was to estimate the combined effects of seawater acidification and temperature increase on the energy budget of the thick shell mussel Mytilus coruscus. Juvenile mussels were exposed to six combined treatments with three pH levels (8.1, 7.7 and 7.3) * two temperatures (25 °C and 30 °C) for 14 d. We found that clearance rates (CRs), food absorption efficiencies (AEs), respiration rates (RRs), ammonium excretion rates (ER), scope for growth (SFG) and O:N ratios were significantly reduced by elevated temperature sometimes during the whole experiments. Low pH showed significant negative effects on RR and ER, and significantly increased O:N ratios, but showed almost no effects on CR, AE and SFG of M. coruscus. Nevertheless, their interactive effects were observed in RR, ER and O:N ratios. PCA revealed positive relationships among most physiological indicators, especially between SFG and CR under normal temperatures compared to high temperatures. PCA also showed that the high RR was closely correlated to an increasing ER with increasing pH levels. These results suggest that physiological energetics of juvenile M. coruscus are able to acclimate to CO2 acidification with a little physiological effect, but not increased temperatures. Therefore, the negative effects of a temperature increase could potentially impact the ecophysiological responses of M. coruscus and have significant ecological consequences, mainly in those habitats where this species is dominant in terms of abundance and biomass.