Pyrolysis, combustion and oxy-combustion studies of sugarcane industry wastes and its blends

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)

O espaço-tempo não comutativo em Teoria Quântica de Campos, Matéria Condensada Mole e Física Biológica

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)

Magnetic Tuning of All-Organic Binary Alloys between Two Stable Radicals

Mixtures of 2-(4,5,6,7-tetrafluorobenzimidazol-2-yl)-4,4,5,5-tetramethyl-4,5-dihydro-1H-imidazole-3-oxide-1-oxyl (F4BImNN) and 2-(benzi-midazol-2-yl)-4,4,5,5-tetramethyl-4,5-dihydro-1H-imidazole-3-oxide-1-oxyl (BImNN.) crystallize as solid solutions (alloys) across a wide range of binary compositions. (F4BImNN)(x)(BImNN)((1-x)) with x < 0.8 gives orthorhombic unit cells, while x >= 0.9 gives monoclinic unit cells. In all crystalline samples, the dominant intermolecular packing is controlled by one-dimensional (1D) hydrogen-bonded chains that lead to quasi-1D ferromagnetic behavior. Magnetic analysis over 0.4-300 K indicates ordering with strong 1D ferromagnetic exchange along the chains (J/k = 12-22 K). Interchain exchange is estimated to be 33- to 150-fold weaker, based on antiferromagnetic ordered phase formation below Neel temperatures in the 0.4-1.2 K range for the various compositions. The ordering temperatures of the orthorhombic samples increase linearly as (1 - x) increases from 0.25 to 1.00. The variation is attributed to increased interchain distance corresponding to decreased interchain exchange, when more F4BImNN is added into the orthorhombic lattice. The monoclinic samples are not part of the same trend, due to the different interchain arrangement associated with the phase change.

Interstitial doping induced superconductivity at 15.3 K in Nb5Ge3 compound

It is reported superconductivity in Nb5Ge3C0.3, an interstitial carbide compound. The temperature dependence of the electrical resistivity, ac-susceptibility, and heat capacity (HC) indicate that a bulk type-II superconductivity appears at T-C - 15.3 K. Magneto-resistance measurements suggest an upper critical field of B-C2 similar to 10.6 T and a coherence length of xi similar to 55 angstrom at zero temperature. Neutron diffraction analyzes locate the carbon atoms at the interstitial 2b site of the Mn5Si3 type-structure. Heat capacity data below T-C are well described by BCS theory. The size of the jump at T-C is in good agreement with the superconducting volume fraction observed in susceptibility measurements. A Debye temperature and Sommerfeld constant were also extracted from heat capacity data as 343 K and 34 mJ/mol K-2, respectively. (C) 2012 American Institute of Physics. [http://dx.doi.org/10.1063/1.4730611]

Study of surface free energy on a lattice-gas model applied to Liquid bridge

The pulmonary crackling and the formation of liquid bridges are problems that for centuries have been attracting the attention of scientists. In order to study these phenomena, it was developed a canonical cubic lattice-gas­ like model to explain the rupture of liquid bridges in lung airways [A. Alencar et al., 2006, PRE]. Here, we further develop this model and add entropy analysis to study thermodynamic properties, such as free energy and force. The simulations were performed using the Monte Carlo method with Metropolis algorithm. The exchange between gas and liquid particles were performed randomly according to the Kawasaki dynamics and weighted by the Boltzmann factor. Each particle, which can be solid (s), liquid (l) or gas (g), has 26 neighbors: 6 + 12 + 8, with distances 1, √2 and √3, respectively. The energy of a lattice's site m is calculated by the following expression: Em = ∑k=126 Ji(m)j(k) in witch (i, j) = g, l or s. Specifically, it was studied the surface free energy of the liquid bridge, trapped between two planes, when its height is changed. For that, was considered two methods. First, just the internal energy was calculated. Then was considered the entropy. It was fond no difference in the surface free energy between this two methods. We calculate the liquid bridge force between the two planes using the numerical surface free energy. This force is strong for small height, and decreases as the distance between the two planes, height, is increased. The liquid-gas system was also characterized studying the variation of internal energy and heat capacity with the temperature. For that, was performed simulation with the same proportion of liquid and gas particle, but different lattice size. The scale of the liquid-gas system was also studied, for low temperature, using different values to the interaction Jij.

Detecting interfaces in a parabolic-elliptic problem from surface measurements

Assuming that the heat capacity of a body is negligible outside certain inclusions the heat equation degenerates to a parabolic-elliptic interface problem. In this work we aim to detect these interfaces from thermal measurements on the surface of the body. We deduce an equivalent variational formulation for the parabolic-elliptic problem and give a new proof of the unique solvability based on Lions’s projection lemma. For the case that the heat conductivity is higher inside the inclusions, we develop an adaptation of the factorization method to this time-dependent problem. In particular this shows that the locations of the interfaces are uniquely determined by boundary measurements. The method also yields to a numerical algorithm to recover the inclusions and thus the interfaces. We demonstrate how measurement data can be simulated numerically by a coupling of a finite element method with a boundary element method, and finally we present some numerical results for the inverse problem.

Wet chemistry synthesis towards nanostructures of thermoelectric antimonides

Die vorliegende Arbeit befasst sich mit der Synthese von nanostrukturierten Antimoniden, wobei die folgenden beiden Themen bearbeitet wurden: rnAus chemischer Sicht wurden neue Synthesewege entwickelt, um Nanopartikel der Verbindungen in den binären Systemen Zn-Sb und Fe-Sb herzustellen (Zn4Sb3, ZnSb, FeSb2, Fe1+xSb). Anders als in konventionellen Festkörperreaktionen, die auf die Synthese von Bulk-Materialien oder Einkristallen zielen, muss die Synthese von Nanopartikeln Agglomerate und Ostwald-Wachstum vermeiden. Daher benötigen annehmbare Reaktionszeiten und vergleichsweise tiefe Reaktionstemperaturen kurze Diffusionswege und tiefe Aktivierungsbarrieren. Demzufolge bedient sich die Synthese der Reaktion von Antimon-Nanopartikeln und geeigneten molekularen oder nanopartikulären Edukten der entsprechenden Übergangsmetalle. Zusätzlich wurden anisotrope ZnSb Strukturen synthetisiert, indem eine Templat-Synthese mit Hilfe von anodisierten Aluminiumoxid- oder Polycarbonat-Membranen angewandt wurde. rnDie erhaltenen Produkte wurden hauptsächlich durch Röntgen-Diffraktion und Elektronenmikroskopie untersucht. Die Auswertung der Pulver Röntgendiffraktions-Daten stellte eine Herausforderung dar, da die Nanostrukturierung und die Anwesenheit von mehreren Phasen zu verbreiterten und überlagernden Reflexen führen. Zusätzliche Fe-Mößbauer Messungen wurden im Falle der Fe-Sb Produkte vorgenommen, um detailliertere Informationen über die genaue Zusammensetzung zu erhalten. Die erstmals hergestellte Phase Zn1+xSb wurde einer detaillierten Kristallstrukturanalyse unterzogen, die mit Hilfe einer neuen Diffraktionsmethode, der automatisierten Elektronen Diffraktions Tomographie, durchgeführt wurde.rnrnAus physikalischer Sicht sind Zn4Sb3, ZnSb und FeSb2 interessante thermoelektrische Materialien, die aufgrund ihrer Fähigkeit thermische in elektrische Energie umzuwandeln, großes Interesse geweckt haben. Nanostrukturierte thermoelektrische Materialien zeigen dabei eine höhere Umwandlungseffizienz zu erhöhen, da deren thermische Leitfähigkeit herabgesetzt ist. Da thermoelektrische Bauteile aus dichten Bulk-Materialien gefertigt werden, spielte die Verfestigung der synthetisierten nanopartikulären Pulver eine große Rolle. Die als „Spark Plasma Sintering“ bezeichnete Methode wurde eingesetzt, um die Proben zu pressen. Dies ermöglicht schnelles Heizen und Abkühlen der Probe und kann so das bei klassischen Heißpress-Methoden unvermeidliche Kristallitwachstum verringern. Die optimalen Bedingungen für das Spark Plasma Sintern zu finden, ist Inhalt von bestehender und weiterführender Forschung. rnEin Problem stellt die Stabilität der Proben während des Sinterns dar. Trotz des schnellen Pressens wurde eine teilweise Zersetzung im Falle des Zn1+xSb beobachtet, wie mit Hilfe von Synchrotrondiffraktionsuntersuchungen aufgedeckt wurde. Morphologie und Dichte der verschiedenen verfestigten Materialien wurden mittels Rasterelektronenmikroskopie und Lasermikroskopie bestimmt. Die Gitterdynamik wurde mit Hilfe von Wärmekapazitätsmessungen- und inelastischer Kern-Streuung untersucht. Die Wärmeleitfähigkeit der nanostrukturierten Materialien ist im Vergleich zu den Festkörpern ist drastisch reduziert - im Falle des FeSb2 um mehr als zwei Größenordnungen. Abhängig von der Zusammensetzung und mechanischen Härte wurden für einen Teil der verfestigten Nanomaterialien die thermoelektrische Eigenschaften, wie Seebeck Koeffizient, elektrische und Wärmeleitfähigkeit, gemessen.rn

Molecular dynamics simulations of silicate and borate glasses and melts : structure, diffusion dynamics and vibrational properties

Molecular dynamics simulations of silicate and borate glasses and melts: Structure, diffusion dynamics and vibrational properties. In this work computer simulations of the model glass formers SiO2 and B2O3 are presented, using the techniques of classical molecular dynamics (MD) simulations and quantum mechanical calculations, based on density functional theory (DFT). The latter limits the system size to about 100−200 atoms. SiO2 and B2O3 are the two most important network formers for industrial applications of oxide glasses. Glass samples are generated by means of a quench from the melt with classical MD simulations and a subsequent structural relaxation with DFT forces. In addition, full ab initio quenches are carried out with a significantly faster cooling rate. In principle, the structural properties are in good agreement with experimental results from neutron and X-ray scattering, in all cases. A special focus is on the study of vibrational properties, as they give access to low-temperature thermodynamic properties. The vibrational spectra are calculated by the so-called ”frozen phonon” method. In all cases, the DFT curves show an acceptable agreement with experimental results of inelastic neutron scattering. In case of the model glass former B2O3, a new classical interaction potential is parametrized, based on the liquid trajectory of an ab initio MD simulation at 2300 K. In this course, a structural fitting routine is used. The inclusion of 3-body angular interactions leads to a significantly improved agreement of the liquid properties of the classical MD and ab initio MD simulations. However, the generated glass structures, in all cases, show a significantly lower fraction of 3-membered planar boroxol rings as predicted by experimental results (f=60%-80%). The largest boroxol ring fraction of f=15±5% is observed in the full ab initio quenches from 2300 K. In case of SiO2, the glass structures after the quantum mechanical relaxation are the basis for calculations of the linear thermal expansion coefficient αL(T), employing the quasi-harmonic approximation. The striking observation is a change change of sign of αL(T) going along with a temperature range of negative αL(T) at low temperatures, which is in good agreement with experimental results.

Distortion-sensitive insight into the pretransitional behavior of 4- n -octyloxy-4′-cyanobiphenyl (8OCB)

Results of studies of the static and dynamic dielectric properties in rod-like 4-n-octyloxy-4'-cyanobiphenyl (8OCB) with isotropic (I)–nematic (N)–smectic A (SmA)–crystal (Cr) mesomorphism, combined with measurements of the low-frequency nonlinear dielectric effect and heat capacity are presented. The analysis is supported by the derivative-based and distortion-sensitive transformation of experimental data. Evidence for the I–N and N–SmA pretransitional anomalies, indicating the influence of tricritical behavior, is shown. It has also been found that neither the N phase nor the SmA phase are uniform and hallmarks of fluid–fluid crossovers can be detected. The dynamics, tested via the evolution of the primary relaxation time, is clearly non-Arrhenius and described via τ(T) = τc(T−TC)−phgr. In the immediate vicinity of the I–N transition a novel anomaly has been found: Δτ ∝ 1/(T − T*), where T* is the temperature of the virtual continuous transition and Δτ is the excess over the 'background behavior'. Experimental results are confronted with the comprehensive Landau–de Gennes theory based modeling.

Standard Model thermodynamics across the electroweak crossover

Even though the Standard Model with a Higgs mass mH = 125GeV possesses no bulk phase transition, its thermodynamics still experiences a "soft point" at temperatures around T = 160GeV, with a deviation from ideal gas thermodynamics. Such a deviation may have an effect on precision computations of weakly interacting dark matter relic abundances if their mass is in the few TeV range, or on leptogenesis scenarios operating in this temperature range. By making use of results from lattice simulations based on a dimensionally reduced effective field theory, we estimate the relevant thermodynamic functions across the crossover. The results are tabulated in a numerical form permitting for their insertion as a background equation of state into cosmological particle production/decoupling codes. We find that Higgs dynamics induces a non-trivial "structure" visible e.g. in the heat capacity, but that in general the largest radiative corrections originate from QCD effects, reducing the energy density by a couple of percent from the free value even at T > 160GeV.

Standard model cross-over on the lattice

With the physical Higgs mass the standard model symmetry restoration phase transition is a smooth cross-over. We study the thermodynamics of the cross-over using numerical lattice Monte Carlo simulations of an effective SU(2)×U(1) gauge+Higgs theory, significantly improving on previously published results. We measure the Higgs field expectation value, thermodynamic quantities like pressure, energy density, speed of sound and heat capacity, and screening masses associated with the Higgs and Z fields. While the cross-over is smooth, it is very well defined with a width of only ∼5  GeV. We measure the cross-over temperature from the maximum of the susceptibility of the Higgs condensate, with the result Tc=159.5±1.5  GeV. Outside of the narrow cross-over region the perturbative results agree well with nonperturbative ones.

The physical properties of basalt at DSDP Hole 45-395A

A detailed study has been made of the physical properties of core samples from Deep Sea Drilling Project Hole 395A. The properties include: density, porosity, compressional and shear wave velocity, thermal conductivity, thermal diffusivity, and electrical resistivity. Of particular importance are the relations among the parameters. Most of the variations in the basalt properties follow the porosity, with smaller inferred dependence on pore structure, original mineralogy differences, and alteration. The sample measurements give very similar results to (and extend previous data from) Mid-Atlantic Ridge drillholes, the sample data from this site and previous data are used to estimate relations between porosity and other large-scale physical properties of the upper oceanic crust applicable to this area. These relations are important for the analysis and interpretation of downhole logging measurements and marine geophysical data.

Climate variability effects on field crops in Iberian Peninsula. Predictability

La presente Tesis constituye un avance en el conocimiento de los efectos de la variabilidad climática en los cultivos en la Península Ibérica (PI). Es bien conocido que la temperatura del océano, particularmente de la región tropical, es una de las variables más convenientes para ser utilizado como predictor climático. Los océanos son considerados como la principal fuente de almacenamiento de calor del planeta debido a la alta capacidad calorífica del agua. Cuando se libera esta energía, altera los regímenes globales de circulación atmosférica por mecanismos de teleconexión. Estos cambios en la circulación general de la atmósfera afectan a la temperatura, precipitación, humedad, viento, etc., a escala regional, los cuales afectan al crecimiento, desarrollo y rendimiento de los cultivos. Para el caso de Europa, esto implica que la variabilidad atmosférica en una región específica se asocia con la variabilidad de otras regiones adyacentes y/o remotas, como consecuencia Europa está siendo afectada por los patrones de circulaciones globales, que a su vez, se ven afectados por patrones oceánicos. El objetivo general de esta tesis es analizar la variabilidad del rendimiento de los cultivos y su relación con la variabilidad climática y teleconexiones, así como evaluar su predictibilidad. Además, esta Tesis tiene como objetivo establecer una metodología para estudiar la predictibilidad de las anomalías del rendimiento de los cultivos. El análisis se centra en trigo y maíz como referencia para otros cultivos de la PI, cultivos de invierno en secano y cultivos de verano en regadío respectivamente. Experimentos de simulación de cultivos utilizando una metodología en cadena de modelos (clima + cultivos) son diseñados para evaluar los impactos de los patrones de variabilidad climática en el rendimiento y su predictibilidad. La presente Tesis se estructura en dos partes: La primera se centra en el análisis de la variabilidad del clima y la segunda es una aplicación de predicción cuantitativa de cosechas. La primera parte está dividida en 3 capítulos y la segundo en un capitulo cubriendo los objetivos específicos del presente trabajo de investigación. Parte I. Análisis de variabilidad climática El primer capítulo muestra un análisis de la variabilidad del rendimiento potencial en una localidad como indicador bioclimático de las teleconexiones de El Niño con Europa, mostrando su importancia en la mejora de predictibilidad tanto en clima como en agricultura. Además, se presenta la metodología elegida para relacionar el rendimiento con las variables atmosféricas y oceánicas. El rendimiento de los cultivos es parcialmente determinado por la variabilidad climática atmosférica, que a su vez depende de los cambios en la temperatura de la superficie del mar (TSM). El Niño es el principal modo de variabilidad interanual de la TSM, y sus efectos se extienden en todo el mundo. Sin embargo, la predictibilidad de estos impactos es controversial, especialmente aquellos asociados con la variabilidad climática Europea, que se ha encontrado que es no estacionaria y no lineal. Este estudio mostró cómo el rendimiento potencial de los cultivos obtenidos a partir de datos de reanálisis y modelos de cultivos sirve como un índice alternativo y más eficaz de las teleconexiones de El Niño, ya que integra las no linealidades entre las variables climáticas en una única serie temporal. Las relaciones entre El Niño y las anomalías de rendimiento de los cultivos son más significativas que las contribuciones individuales de cada una de las variables atmosféricas utilizadas como entrada en el modelo de cultivo. Además, la no estacionariedad entre El Niño y la variabilidad climática europea se detectan con mayor claridad cuando se analiza la variabilidad de los rendimiento de los cultivos. La comprensión de esta relación permite una cierta predictibilidad hasta un año antes de la cosecha del cultivo. Esta predictibilidad no es constante, sino que depende tanto la modulación de la alta y baja frecuencia. En el segundo capítulo se identifica los patrones oceánicos y atmosféricos de variabilidad climática que afectan a los cultivos de verano en la PI. Además, se presentan hipótesis acerca del mecanismo eco-fisiológico a través del cual el cultivo responde. Este estudio se centra en el análisis de la variabilidad del rendimiento de maíz en la PI para todo el siglo veinte, usando un modelo de cultivo calibrado en 5 localidades españolas y datos climáticos de reanálisis para obtener series temporales largas de rendimiento potencial. Este estudio evalúa el uso de datos de reanálisis para obtener series de rendimiento de cultivos que dependen solo del clima, y utilizar estos rendimientos para analizar la influencia de los patrones oceánicos y atmosféricos. Los resultados muestran una gran fiabilidad de los datos de reanálisis. La distribución espacial asociada a la primera componente principal de la variabilidad del rendimiento muestra un comportamiento similar en todos los lugares estudiados de la PI. Se observa una alta correlación lineal entre el índice de El Niño y el rendimiento, pero no es estacionaria en el tiempo. Sin embargo, la relación entre la temperatura del aire y el rendimiento se mantiene constante a lo largo del tiempo, siendo los meses de mayor influencia durante el período de llenado del grano. En cuanto a los patrones atmosféricos, el patrón Escandinavia presentó una influencia significativa en el rendimiento en PI. En el tercer capítulo se identifica los patrones oceánicos y atmosféricos de variabilidad climática que afectan a los cultivos de invierno en la PI. Además, se presentan hipótesis acerca del mecanismo eco-fisiológico a través del cual el cultivo responde. Este estudio se centra en el análisis de la variabilidad del rendimiento de trigo en secano del Noreste (NE) de la PI. La variabilidad climática es el principal motor de los cambios en el crecimiento, desarrollo y rendimiento de los cultivos, especialmente en los sistemas de producción en secano. En la PI, los rendimientos de trigo son fuertemente dependientes de la cantidad de precipitación estacional y la distribución temporal de las mismas durante el periodo de crecimiento del cultivo. La principal fuente de variabilidad interanual de la precipitación en la PI es la Oscilación del Atlántico Norte (NAO), que se ha relacionado, en parte, con los cambios en la temperatura de la superficie del mar en el Pacífico Tropical (El Niño) y el Atlántico Tropical (TNA). La existencia de cierta predictibilidad nos ha animado a analizar la posible predicción de los rendimientos de trigo en la PI utilizando anomalías de TSM como predictor. Para ello, se ha utilizado un modelo de cultivo (calibrado en dos localidades del NE de la PI) y datos climáticos de reanálisis para obtener series temporales largas de rendimiento de trigo alcanzable y relacionar su variabilidad con anomalías de la TSM. Los resultados muestran que El Niño y la TNA influyen en el desarrollo y rendimiento del trigo en el NE de la PI, y estos impactos depende del estado concurrente de la NAO. Aunque la relación cultivo-TSM no es igual durante todo el periodo analizado, se puede explicar por un mecanismo eco-fisiológico estacionario. Durante la segunda mitad del siglo veinte, el calentamiento (enfriamiento) en la superficie del Atlántico tropical se asocia a una fase negativa (positiva) de la NAO, que ejerce una influencia positiva (negativa) en la temperatura mínima y precipitación durante el invierno y, por lo tanto, aumenta (disminuye) el rendimiento de trigo en la PI. En relación con El Niño, la correlación más alta se observó en el período 1981 -2001. En estas décadas, los altos (bajos) rendimientos se asocian con una transición El Niño - La Niña (La Niña - El Niño) o con eventos de El Niño (La Niña) que están finalizando. Para estos eventos, el patrón atmosférica asociada se asemeja a la NAO, que también influye directamente en la temperatura máxima y precipitación experimentadas por el cultivo durante la floración y llenado de grano. Los co- efectos de los dos patrones de teleconexión oceánicos ayudan a aumentar (disminuir) la precipitación y a disminuir (aumentar) la temperatura máxima en PI, por lo tanto el rendimiento de trigo aumenta (disminuye). Parte II. Predicción de cultivos. En el último capítulo se analiza los beneficios potenciales del uso de predicciones climáticas estacionales (por ejemplo de precipitación) en las predicciones de rendimientos de trigo y maíz, y explora métodos para aplicar dichos pronósticos climáticos en modelos de cultivo. Las predicciones climáticas estacionales tienen un gran potencial en las predicciones de cultivos, contribuyendo de esta manera a una mayor eficiencia de la gestión agrícola, seguridad alimentaria y de subsistencia. Los pronósticos climáticos se expresan en diferentes formas, sin embargo todos ellos son probabilísticos. Para ello, se evalúan y aplican dos métodos para desagregar las predicciones climáticas estacionales en datos diarios: 1) un generador climático estocástico condicionado (predictWTD) y 2) un simple re-muestreador basado en las probabilidades del pronóstico (FResampler1). Los dos métodos se evaluaron en un caso de estudio en el que se analizaron los impactos de tres escenarios de predicciones de precipitación estacional (predicción seco, medio y lluvioso) en el rendimiento de trigo en secano, sobre las necesidades de riego y rendimiento de maíz en la PI. Además, se estimó el margen bruto y los riesgos de la producción asociada con las predicciones de precipitación estacional extremas (seca y lluviosa). Los métodos predWTD y FResampler1 usados para desagregar los pronósticos de precipitación estacional en datos diarios, que serán usados como inputs en los modelos de cultivos, proporcionan una predicción comparable. Por lo tanto, ambos métodos parecen opciones factibles/viables para la vinculación de los pronósticos estacionales con modelos de simulación de cultivos para establecer predicciones de rendimiento o las necesidades de riego en el caso de maíz. El análisis del impacto en el margen bruto de los precios del grano de los dos cultivos (trigo y maíz) y el coste de riego (maíz) sugieren que la combinación de los precios de mercado previstos y la predicción climática estacional pueden ser una buena herramienta en la toma de decisiones de los agricultores, especialmente en predicciones secas y/o localidades con baja precipitación anual. Estos métodos permiten cuantificar los beneficios y riesgos de los agricultores ante una predicción climática estacional en la PI. Por lo tanto, seríamos capaces de establecer sistemas de alerta temprana y diseñar estrategias de adaptación del manejo del cultivo para aprovechar las condiciones favorables o reducir los efectos de condiciones adversas. La utilidad potencial de esta Tesis es la aplicación de las relaciones encontradas para predicción de cosechas de la próxima campaña agrícola. Una correcta predicción de los rendimientos podría ayudar a los agricultores a planear con antelación sus prácticas agronómicas y todos los demás aspectos relacionados con el manejo de los cultivos. Esta metodología se puede utilizar también para la predicción de las tendencias futuras de la variabilidad del rendimiento en la PI. Tanto los sectores públicos (mejora de la planificación agrícola) como privados (agricultores, compañías de seguros agrarios) pueden beneficiarse de esta mejora en la predicción de cosechas. ABSTRACT The present thesis constitutes a step forward in advancing of knowledge of the effects of climate variability on crops in the Iberian Peninsula (IP). It is well known that ocean temperature, particularly the tropical ocean, is one of the most convenient variables to be used as climate predictor. Oceans are considered as the principal heat storage of the planet due to the high heat capacity of water. When this energy is released, it alters the global atmospheric circulation regimes by teleconnection1 mechanisms. These changes in the general circulation of the atmosphere affect the regional temperature, precipitation, moisture, wind, etc., and those influence crop growth, development and yield. For the case of Europe, this implies that the atmospheric variability in a specific region is associated with the variability of others adjacent and/or remote regions as a consequence of Europe being affected by global circulations patterns which, in turn, are affected by oceanic patterns. The general objective of this Thesis is to analyze the variability of crop yields at climate time scales and its relation to the climate variability and teleconnections, as well as to evaluate their predictability. Moreover, this Thesis aims to establish a methodology to study the predictability of crop yield anomalies. The analysis focuses on wheat and maize as a reference crops for other field crops in the IP, for winter rainfed crops and summer irrigated crops respectively. Crop simulation experiments using a model chain methodology (climate + crop) are designed to evaluate the impacts of climate variability patterns on yield and its predictability. The present Thesis is structured in two parts. The first part is focused on the climate variability analyses, and the second part is an application of the quantitative crop forecasting for years that fulfill specific conditions identified in the first part. This Thesis is divided into 4 chapters, covering the specific objectives of the present research work. Part I. Climate variability analyses The first chapter shows an analysis of potential yield variability in one location, as a bioclimatic indicator of the El Niño teleconnections with Europe, putting forward its importance for improving predictability in both climate and agriculture. It also presents the chosen methodology to relate yield with atmospheric and oceanic variables. Crop yield is partially determined by atmospheric climate variability, which in turn depends on changes in the sea surface temperature (SST). El Niño is the leading mode of SST interannual variability, and its impacts extend worldwide. Nevertheless, the predictability of these impacts is controversial, especially those associated with European climate variability, which have been found to be non-stationary and non-linear. The study showed how potential2 crop yield obtained from reanalysis data and crop models serves as an alternative and more effective index of El Niño teleconnections because it integrates the nonlinearities between the climate variables in a unique time series. The relationships between El Niño and crop yield anomalies are more significant than the individual contributions of each of the atmospheric variables used as input in the crop model. Additionally, the non-stationarities between El Niño and European climate variability are more clearly detected when analyzing crop-yield variability. The understanding of this relationship allows for some predictability up to one year before the crop is harvested. This predictability is not constant, but depends on both high and low frequency modulation. The second chapter identifies the oceanic and atmospheric patterns of climate variability affecting summer cropping systems in the IP. Moreover, hypotheses about the eco-physiological mechanism behind crop response are presented. It is focused on an analysis of maize yield variability in IP for the whole twenty century, using a calibrated crop model at five contrasting Spanish locations and reanalyses climate datasets to obtain long time series of potential yield. The study tests the use of reanalysis data for obtaining only climate dependent time series of simulated crop yield for the whole region, and to use these yield to analyze the influences of oceanic and atmospheric patterns. The results show a good reliability of reanalysis data. The spatial distribution of the leading principal component of yield variability shows a similar behaviour over all the studied locations in the IP. The strong linear correlation between El Niño index and yield is remarkable, being this relation non-stationary on time, although the air temperature-yield relationship remains on time, being the highest influences during grain filling period. Regarding atmospheric patterns, the summer Scandinavian pattern has significant influence on yield in IP. The third chapter identifies the oceanic and atmospheric patterns of climate variability affecting winter cropping systems in the IP. Also, hypotheses about the eco-physiological mechanism behind crop response are presented. It is focused on an analysis of rainfed wheat yield variability in IP. Climate variability is the main driver of changes in crop growth, development and yield, especially for rainfed production systems. In IP, wheat yields are strongly dependent on seasonal rainfall amount and temporal distribution of rainfall during the growing season. The major source of precipitation interannual variability in IP is the North Atlantic Oscillation (NAO) which has been related in part with changes in the Tropical Pacific (El Niño) and Atlantic (TNA) sea surface temperature (SST). The existence of some predictability has encouraged us to analyze the possible predictability of the wheat yield in the IP using SSTs anomalies as predictor. For this purpose, a crop model with a site specific calibration for the Northeast of IP and reanalysis climate datasets have been used to obtain long time series of attainable wheat yield and relate their variability with SST anomalies. The results show that El Niño and TNA influence rainfed wheat development and yield in IP and these impacts depend on the concurrent state of the NAO. Although crop-SST relationships do not equally hold on during the whole analyzed period, they can be explained by an understood and stationary ecophysiological mechanism. During the second half of the twenty century, the positive (negative) TNA index is associated to a negative (positive) phase of NAO, which exerts a positive (negative) influence on minimum temperatures (Tmin) and precipitation (Prec) during winter and, thus, yield increases (decreases) in IP. In relation to El Niño, the highest correlation takes place in the period 1981-2001. For these decades, high (low) yields are associated with an El Niño to La Niña (La Niña to El Niño) transitions or to El Niño events finishing. For these events, the regional associated atmospheric pattern resembles the NAO, which also influences directly on the maximum temperatures (Tmax) and precipitation experienced by the crop during flowering and grain filling. The co-effects of the two teleconnection patterns help to increase (decrease) the rainfall and decrease (increase) Tmax in IP, thus on increase (decrease) wheat yield. Part II. Crop forecasting The last chapter analyses the potential benefits for wheat and maize yields prediction from using seasonal climate forecasts (precipitation), and explores methods to apply such a climate forecast to crop models. Seasonal climate prediction has significant potential to contribute to the efficiency of agricultural management, and to food and livelihood security. Climate forecasts come in different forms, but probabilistic. For this purpose, two methods were evaluated and applied for disaggregating seasonal climate forecast into daily weather realizations: 1) a conditioned stochastic weather generator (predictWTD) and 2) a simple forecast probability resampler (FResampler1). The two methods were evaluated in a case study where the impacts of three scenarios of seasonal rainfall forecasts on rainfed wheat yield, on irrigation requirements and yields of maize in IP were analyzed. In addition, we estimated the economic margins and production risks associated with extreme scenarios of seasonal rainfall forecasts (dry and wet). The predWTD and FResampler1 methods used for disaggregating seasonal rainfall forecast into daily data needed by the crop simulation models provided comparable predictability. Therefore both methods seem feasible options for linking seasonal forecasts with crop simulation models for establishing yield forecasts or irrigation water requirements. The analysis of the impact on gross margin of grain prices for both crops and maize irrigation costs suggests the combination of market prices expected and the seasonal climate forecast can be a good tool in farmer’s decision-making, especially on dry forecast and/or in locations with low annual precipitation. These methodologies would allow quantifying the benefits and risks of a seasonal weather forecast to farmers in IP. Therefore, we would be able to establish early warning systems and to design crop management adaptation strategies that take advantage of favorable conditions or reduce the effect of adverse conditions. The potential usefulness of this Thesis is to apply the relationships found to crop forecasting on the next cropping season, suggesting opportunity time windows for the prediction. The methodology can be used as well for the prediction of future trends of IP yield variability. Both public (improvement of agricultural planning) and private (decision support to farmers, insurance companies) sectors may benefit from such an improvement of crop forecasting.

Membrane-bound state of the colicin E1 channel domain as an extended two-dimensional helical array

Atomic level structures have been determined for the soluble forms of several colicins and toxins, but the structural changes that occur after membrane binding have not been well characterized. Changes occurring in the transition from the soluble to membrane-bound state of the C-terminal 190-residue channel polypeptide of colicin E1 (P190) bound to anionic membranes are described. In the membrane-bound state, the α-helical content increases from 60–64% to 80–90%, with a concomitant increase in the average length of the helical segments from 12 to 16 or 17 residues, close to the length required to span the membrane bilayer in the open channel state. The average distance between helical segments is increased and interhelix interactions are weakened, as shown by a major loss of tertiary structure interactions, decreased efficiency of fluorescence resonance energy transfer from an energy donor on helix V of P190 to an acceptor on helix IX, and decreased resonance energy transfer at higher temperatures, not observed in soluble P190, implying freedom of motion of helical segments. Weaker interactions are also shown by a calorimetric thermal transition of low cooperativity, and the extended nature of the helical array is shown by a 3- to 4-fold increase in the average area subtended per molecule to 4,200 Å2 on the membrane surface. The latter, with analysis of the heat capacity changes, implies the absence of a developed hydrophobic core in the membrane-bound P190. The membrane interfacial layer thus serves to promote formation of a highly helical extended two-dimensional flexible net. The properties of the membrane-bound state of the colicin channel domain (i.e., hydrophobic anchor, lengthened and loosely coupled α-helices, and close association with the membrane interfacial layer) are plausible structural features for the state that is a prerequisite for voltage gating, formation of transmembrane helices, and channel opening.