Time-dependent interactions of the two porphyrinic compounds chlorin e6 and mono-L-aspartyl-chlorin e6 with phospholipid vesicles probed by NMR spectroscopy

The distribution processes of chlorin e6 (CE) and monoaspartyl-chlorin e6 (MACE) between the outer and inner phospholipid monolayers of 1,2-dioleoyl-phosphatidylcholine (DOPC) vesicles were monitored by 1H NMR spectroscopy through analysis of chemical shifts and line widths of the DOPC vesicle resonances. Chlorin adsorption to the outer vesicle monolayer induced changes in the DOPC 1H NMR spectrum. Most pronounced was a split of the N-methyl choline resonance, allowing for separate analysis of inner and outer vesicle layers. Transbilayer distribution of the chlorin compounds was indicated by time-dependent characteristic spectral changes of the DOPC resonances. Kinetic parameters for the flip-flop processes, that is, half-lives and rate constants, were obtained from the experimental data points. In comparison to CE, MACE transbilayer movement was significantly reduced, with MACE remaining more or less attached to the outer membrane layer. The distribution coefficients for CE and MACE between the vesicular and aqueous phase were determined. Both CE and MACE exhibited a high affinity for the vesicular phase. For CE, a positive correlation was found between transfer rate and increasing molar ratio CE/DOPC. Enhanced membrane rigidity induced by increasing amounts of cholesterol into the model membrane was accompanied by a decrease of CE flip-flop rates across the membrane. The present study shows that the movement of porphyrins across membranes can efficiently be investigated by 1H NMR spectroscopy and that small changes in porphyrin structure can have large effects on membrane kinetics.

Prediction of PA12 melt viscosity in Laser Sintering by a Time and Temperature dependent rheological model

Ein auf Basis von Prozessdaten kalibriertes Viskositätsmodell wird vorgeschlagen und zur Vorhersage der Viskosität einer Polyamid 12 (PA12) Kunststoffschmelze als Funktion von Zeit, Temperatur und Schergeschwindigkeit angewandt. Im ersten Schritt wurde das Viskositätsmodell aus experimentellen Daten abgeleitet. Es beruht hauptsächlich auf dem drei-parametrigen Ansatz von Carreau, wobei zwei zusätzliche Verschiebungsfaktoren eingesetzt werden. Die Temperaturabhängigkeit der Viskosität wird mithilfe des Verschiebungsfaktors aT von Arrhenius berücksichtigt. Ein weiterer Verschiebungsfaktor aSC (Structural Change) wird eingeführt, der die Strukturänderung von PA12 als Folge der Prozessbedingungen beim Lasersintern beschreibt. Beobachtet wurde die Strukturänderung in Form einer signifikanten Viskositätserhöhung. Es wurde geschlussfolgert, dass diese Viskositätserhöhung auf einen Molmassenaufbau zurückzuführen ist und als Nachkondensation verstanden werden kann. Abhängig von den Zeit- und Temperaturbedingungen wurde festgestellt, dass die Viskosität als Folge des Molmassenaufbaus exponentiell gegen eine irreversible Grenze strebt. Die Geschwindigkeit dieser Nachkondensation ist zeit- und temperaturabhängig. Es wird angenommen, dass die Pulverbetttemperatur einen Molmassenaufbau verursacht und es damit zur Kettenverlängerung kommt. Dieser fortschreitende Prozess der zunehmenden Kettenlängen setzt molekulare Beweglichkeit herab und unterbindet die weitere Nachkondensation. Der Verschiebungsfaktor aSC drückt diese physikalisch-chemische Modellvorstellung aus und beinhaltet zwei zusätzliche Parameter. Der Parameter aSC,UL entspricht der oberen Viskositätsgrenze, wohingegen k0 die Strukturänderungsrate angibt. Es wurde weiterhin festgestellt, dass es folglich nützlich ist zwischen einer Fließaktivierungsenergie und einer Strukturänderungsaktivierungsenergie für die Berechnung von aT und aSC zu unterscheiden. Die Optimierung der Modellparameter erfolgte mithilfe eines genetischen Algorithmus. Zwischen berechneten und gemessenen Viskositäten wurde eine gute Übereinstimmung gefunden, so dass das Viskositätsmodell in der Lage ist die Viskosität einer PA12 Kunststoffschmelze als Folge eines kombinierten Lasersinter Zeit- und Temperatureinflusses vorherzusagen. Das Modell wurde im zweiten Schritt angewandt, um die Viskosität während des Lasersinter-Prozesses in Abhängigkeit von der Energiedichte zu berechnen. Hierzu wurden Prozessdaten, wie Schmelzetemperatur und Belichtungszeit benutzt, die mithilfe einer High-Speed Thermografiekamera on-line gemessen wurden. Abschließend wurde der Einfluss der Strukturänderung auf das Viskositätsniveau im Prozess aufgezeigt.

Relative Predicativity and dependent recursion in second-order set theory and higher-orders theories

This article reports that some robustness of the notions of predicativity and of autonomous progression is broken down if as the given infinite total entity we choose some mathematical entities other than the traditional ω. Namely, the equivalence between normal transfinite recursion scheme and new dependent transfinite recursion scheme, which does hold in the context of subsystems of second order number theory, does not hold in the context of subsystems of second order set theory where the universe V of sets is treated as the given totality (nor in the contexts of those of n+3-th order number or set theories, where the class of all n+2-th order objects is treated as the given totality).

Specific conductivity and hydrogen ions measured on two ice core (NEEM and NGRIP)

A stratigraphy-based chronology for the North Greenland Eemian Ice Drilling (NEEM) ice core has been derived by transferring the annual layer counted Greenland Ice Core Chronology 2005 (GICC05) and its model extension (GICC05modelext) from the NGRIP core to the NEEM core using 787 match points of mainly volcanic origin identified in the electrical conductivity measurement (ECM) and dielectrical profiling (DEP) records. Tephra horizons found in both the NEEM and NGRIP ice cores are used to test the matching based on ECM and DEP and provide five additional horizons used for the timescale transfer. A thinning function reflecting the accumulated strain along the core has been determined using a Dansgaard-Johnsen flow model and an isotope-dependent accumulation rate parameterization. Flow parameters are determined from Monte Carlo analysis constrained by the observed depth-age horizons. In order to construct a chronology for the gas phase, the ice age-gas age difference (Delta age) has been reconstructed using a coupled firn densification-heat diffusion model. Temperature and accumulation inputs to the Delta age model, initially derived from the water isotope proxies, have been adjusted to optimize the fit to timing constraints from d15N of nitrogen and high-resolution methane data during the abrupt onset of Greenland interstadials. The ice and gas chronologies and the corresponding thinning function represent the first chronology for the NEEM core, named GICC05modelext-NEEM-1. Based on both the flow and firn modelling results, the accumulation history for the NEEM site has been reconstructed. Together, the timescale and accumulation reconstruction provide the necessary basis for further analysis of the records from NEEM.

Diatoms on the lower surface of Arctic sea ice and hydrochemical parameters in the water-ice layer

Morphology, ecology, range and species composition of diatom algae mass accumulations that are biotypically associated with the lower surface of Arctic sea ice are discussed. Materials were obtained by skindivers in the Central Arctic Basin at drift stations SP-23 in August 1977 and SP-22 in July 1980.

Parameters of the near-bottom nepheloid layer off the northwestern Africa coast

Vertical profiles of light scattering at a right angle and turbidity profiles in seawater indicating suspended matter concentration in the near-bottom nepheloid layer (NNL) were measured simultaneously with temperature, salinity, and density profiles at the continental slope off the northwestern Africa. About 100 stations 5' apart in latitude and longitude were carried out over an ocean area of 6100 sq. km. Special features of the NNL variability in the area were analyzed. It was found that some structural parameters of the NNL (maximum transparency depth, that is the upper boundary of NNL; NNL thickness; maximum and total turbidity) correlate with ocean depth. On the average, thickness of the NNL in the area is 20-40% of the ocean depth. At most stations the NNL is fairly strong. In the shelf region NNL turbidity was influenced by the intensive near-shore upwelling. Formation of ''high-energy near-bottom layers'' in the shelf region resulted from passing of a mesoscale cyclonic eddy that caused redistribution of measured quantities within the entire water column.

Dinoflagellate cyst assemblages, Mg/Ca based reconstructed temperatures, stable carbon isotopes, and geochemical parameters of sediment core GeoB9508-5

In order to investigate a possible connection between tropical northeast (NE) Atlantic primary productivity, Atlantic meridional overturning circulation (AMOC), and drought in the Sahel region during Heinrich Stadial 1 (HS1), we used dinoflagellate cyst (dinocyst) assemblages, Mg/Ca based reconstructed temperatures, stable carbon isotopes (d13C) and geochemical parameters of a marine sediment core (GeoB 9508-5) from the continental slope offshore Senegal. Our results show a two-phase productivity pattern within HS1 that progressed from an interval of low marine productivity between ~ 19 and 16 kyr BP to a phase with an abrupt and large productivity increase from ~ 16 to 15 kyr BP. The second phase is characterized by distinct heavy planktonic d13C values and high concentrations of heterotrophic dinocysts in addition to a significant cooling signal based on reconstructions of past sea surface temperatures (SST). We conclude that productivity variations within HS1 can be attributed to a substantial shift of West African atmospheric processes. Taken together our results indicate a significant intensification of the North East (NE) trade winds over West Africa leading to more intense upwelling during the last millennium of HS1 between ~ 16 and 15 kyr BP, thus leaving a strong imprint on the dinocyst assemblages and sea surface conditions. Therefore, the two-phase productivity pattern indicates a complex hydrographic setting suggesting that HS1 cannot be regarded as uniform as previously thought.

Phytoplankton composition and biomass and its fluorescence parameters in waters of the Nha Trang Bay, South China Sea

Species composition and abundance of phytoplankton and chlorophyll concentration were measured at three horizons of 9 stations in the Nha Trang Bay of the South China Sea in March 1998. Vertical distribution of fluorescence parameters, temperature and irradiance were measured in the 0-18 m layer of the water column at 21 stations. It was shown that according to biomass (B) and chlorophyll concentration (Chl) the Bay is mezotrophic. B and Chl in the water column increased seaward. Mean values of Chl in the southern part of the Bay exceeded those in northern part. Mean values of B were similar. B and Chl in the bottom layer exceeded ones in the upper layer. Diatoms dominated in species diversity and abundance. Diatom Guinardia striata made the main contribution to phytoplankton biomass. Similarity of phytoplankton was high. In the upper layer phytoplankton was photoinhibited during the most part of the light period, but at the bottom photosynthetic activity was high. Water column B varied in an order of magnitude during the daily cycle mainly because of B variations in the bottom layer due to tide flow.

Electromagnetic Instability Studies in Fusion Plasmas Edge

Este trabajo esta dedicado al estudio de las estructuras macroscópicas conocidas en la literatura como filamentos o blobs que han sido observadas de manera universal en el borde de todo tipo de dispositivos de fusión por confinamiento magnético. Estos filamentos, celdas convectivas elongadas a lo largo de las líneas de campo que surgen en el plasma fuertemente turbulento que existe en este tipo de dispositivos, parecen dominar el transporte radial de partículas y energía en la región conocida como Scrape-off Layer, en la que las líneas de campo dejan de estar cerradas y el plasma es dirigido hacia la pared sólida que forma la cámara de vacío. Aunque el comportamiento y las leyes de escala de estas estructuras son relativamente bien conocidos, no existe aún una teoría generalmente aceptada acerca del mecanismo físico responsable de su formación, que constituye una de las principales incógnitas de la teoría de transporte del borde en plasmas de fusión y una cuestión de gran importancia práctica en el desarrollo de la siguiente generación de reactores de fusión (incluyendo dispositivos como ITER y DEMO), puesto que la eficiencia del confinamiento y la cantidad de energía depositadas en la pared dependen directamente de las características del transporte en el borde. El trabajo ha sido realizado desde una perspectiva eminentemente experimental, incluyendo la observación y el análisis de este tipo de estructuras en el stellarator tipo heliotrón LHD (un dispositivo de gran tamaño, capaz de generar plasmas de características cercanas a las necesarias en un reactor de fusión) y en el stellarator tipo heliac TJ-II (un dispositivo de medio tamaño, capaz de generar plasmas relativamente más fríos pero con una accesibilidad y disponibilidad de diagnósticos mayor). En particular, en LHD se observó la generación de filamentos durante las descargas realizadas en configuración de alta _ (alta presión cinética frente a magnética) mediante una cámara visible ultrarrápida, se caracterizó su comportamiento y se investigó, mediante el análisis estadístico y la comparación con modelos teóricos, el posible papel de la Criticalidad Autoorganizada en la formación de este tipo de estructuras. En TJ-II se diseñó y construyó una cabeza de sonda capaz de medir simultáneamente las fluctuaciones electrostáticas y electromagnéticas del plasma. Gracias a este nuevo diagnóstico se pudieron realizar experimentos con el fin de determinar la presencia de corriente paralela a través de los filamentos (un parámetro de gran importancia en su modelización) y relacionar los dos tipos de fluctuaciones por primera vez en un stellarator. Así mismo, también por primera vez en este tipo de dispositivo, fue posible realizar mediciones simultáneas de los tensores viscoso y magnético (Reynolds y Maxwell) de transporte de cantidad de movimiento. ABSTRACT This work has been devoted to the study of the macroscopic structures known in the literature as filaments or blobs, which have been observed universally in the edge of all kind of magnetic confinement fusion devices. These filaments, convective cells stretching along the magnetic field lines, arise from the highly turbulent plasma present in this kind of machines and seem to dominate radial transport of particles and energy in the region known as Scrapeoff Layer, in which field lines become open and plasma is directed towards the solid wall of the vacuum vessel. Although the behavior and scale laws of these structures are relatively well known, there is no generally accepted theory about the physical mechanism involved in their formation yet, which remains one of the main unsolved questions in the fusion plasmas edge transport theory and a matter of great practical importance for the development of the next generation of fusion reactors (including ITER and DEMO), since efficiency of confinement and the energy deposition levels on the wall are directly dependent of the characteristics of edge transport. This work has been realized mainly from an experimental perspective, including the observation and analysis of this kind of structures in the heliotron stellarator LHD (a large device capable of generating reactor-relevant plasma conditions) and in the heliac stellarator TJ-II (a medium-sized device, capable of relatively colder plasmas, but with greater ease of access and diagnostics availability). In particular, in LHD, the generation of filaments during high _ discharges (with high kinetic to magnetic pressure ratio) was observed by means of an ultrafast visible camera, and the behavior of this structures was characterized. Finally, the potential role of Self-Organized Criticality in the generation of filaments was investigated. In TJ-II, a probe head capable of measuring simultaneously electrostatic and electromagnetic fluctuations in the plasma was designed and built. Thanks to this new diagnostic, experiments were carried out in order to determine the presence of parallel current through filaments (one of the most important parameters in their modelization) and to related electromagnetic (EM) and electrostatic (ES) fluctuations for the first time in an stellarator. As well, also for the first time in this kind of device, measurements of the viscous and magnetic momentum transfer tensors (Reynolds and Maxwell) were performed.

Coupled model of initiation and propagation of corrosion in reinforced concrete

Corrosion of reinforcing steel in concrete due to chloride ingress is one of the main causes of the deterioration of reinforced concrete structures. Structures most affected by such a corrosion are marine zone buildings and structures exposed to de-icing salts like highways and bridges. Such process is accompanied by an increase in volume of the corrosión products on the rebarsconcrete interface. Depending on the level of oxidation, iron can expand as much as six times its original volume. This increase in volume exerts tensile stresses in the surrounding concrete which result in cracking and spalling of the concrete cover if the concrete tensile strength is exceeded. The mechanism by which steel embedded in concrete corrodes in presence of chloride is the local breakdown of the passive layer formed in the highly alkaline condition of the concrete. It is assumed that corrosion initiates when a critical chloride content reaches the rebar surface. The mathematical formulation idealized the corrosion sequence as a two-stage process: an initiation stage, during which chloride ions penetrate to the reinforcing steel surface and depassivate it, and a propagation stage, in which active corrosion takes place until cracking of the concrete cover has occurred. The aim of this research is to develop computer tools to evaluate the duration of the service life of reinforced concrete structures, considering both the initiation and propagation periods. Such tools must offer a friendly interface to facilitate its use by the researchers even though their background is not in numerical simulation. For the evaluation of the initiation period different tools have been developed: Program TavProbabilidade: provides means to carry out a probability analysis of a chloride ingress model. Such a tool is necessary due to the lack of data and general uncertainties associated with the phenomenon of the chloride diffusion. It differs from the deterministic approach because it computes not just a chloride profile at a certain age, but a range of chloride profiles for each probability or occurrence. Program TavProbabilidade_Fiabilidade: carries out reliability analyses of the initiation period. It takes into account the critical value of the chloride concentration on the steel that causes breakdown of the passive layer and the beginning of the propagation stage. It differs from the deterministic analysis in that it does not predict if the corrosion is going to begin or not, but to quantifies the probability of corrosion initiation. Program TavDif_1D: was created to do a one dimension deterministic analysis of the chloride diffusion process by the finite element method (FEM) which numerically solves Fick’second Law. Despite of the different FEM solver already developed in one dimension, the decision to create a new code (TavDif_1D) was taken because of the need to have a solver with friendly interface for pre- and post-process according to the need of IETCC. An innovative tool was also developed with a systematic method devised to compare the ability of the different 1D models to predict the actual evolution of chloride ingress based on experimental measurements, and also to quantify the degree of agreement of the models with each others. For the evaluation of the entire service life of the structure: a computer program has been developed using finite elements method to do the coupling of both service life periods: initiation and propagation. The program for 2D (TavDif_2D) allows the complementary use of two external programs in a unique friendly interface: • GMSH - an finite element mesh generator and post-processing viewer • OOFEM – a finite element solver. This program (TavDif_2D) is responsible to decide in each time step when and where to start applying the boundary conditions of fracture mechanics module in function of the amount of chloride concentration and corrosion parameters (Icorr, etc). This program is also responsible to verify the presence and the degree of fracture in each element to send the Information of diffusion coefficient variation with the crack width. • GMSH - an finite element mesh generator and post-processing viewer • OOFEM – a finite element solver. The advantages of the FEM with the interface provided by the tool are: • the flexibility to input the data such as material property and boundary conditions as time dependent function. • the flexibility to predict the chloride concentration profile for different geometries. • the possibility to couple chloride diffusion (initiation stage) with chemical and mechanical behavior (propagation stage). The OOFEM code had to be modified to accept temperature, humidity and the time dependent values for the material properties, which is necessary to adequately describe the environmental variations. A 3-D simulation has been performed to simulate the behavior of the beam on both, action of the external load and the internal load caused by the corrosion products, using elements of imbedded fracture in order to plot the curve of the deflection of the central region of the beam versus the external load to compare with the experimental data.

Fertilization Management: Assessing New Techniques and Key Interactions to Increase Crop Yields With Less N2O Emissions

El óxido nitroso (N2O) es un potente gas de efecto invernadero (GHG) proveniente mayoritariamente de la fertilización nitrogenada de los suelos agrícolas. Identificar estrategias de manejo de la fertilización que reduzcan estas emisiones sin suponer un descenso de los rendimientos es vital tanto a nivel económico como medioambiental. Con ese propósito, en esta Tesis se han evaluado: (i) estrategias de manejo directo de la fertilización (inhibidores de la nitrificación/ureasa); y (ii) interacciones de los fertilizantes con (1) el manejo del agua, (2) residuos de cosecha y (3) diferentes especies de plantas. Para conseguirlo se llevaron a cabo meta-análisis, incubaciones de laboratorio, ensayos en invernadero y experimentos de campo. Los inhibidores de la nitrificación y de la actividad ureasa se proponen habitualmente como medidas para reducir las pérdidas de nitrógeno (N), por lo que su aplicación estaría asociada al uso eficiente del N por parte de los cultivos (NUE). Sin embargo, su efecto sobre los rendimientos es variable. Con el objetivo de evaluar en una primera fase su efectividad para incrementar el NUE y la productividad de los cultivos, se llevó a cabo un meta-análisis. Los inhibidores de la nitrificación dicyandiamide (DCD) y 3,4-dimetilepyrazol phosphate (DMPP) y el inhibidor de la ureasa N-(n-butyl) thiophosphoric triamide (NBPT) fueron seleccionados para el análisis ya que generalmente son considerados las mejores opciones disponibles comercialmente. Nuestros resultados mostraron que su uso puede ser recomendado con el fin de incrementar tanto el rendimiento del cultivo como el NUE (incremento medio del 7.5% y 12.9%, respectivamente). Sin embargo, se observó que su efectividad depende en gran medida de los factores medioambientales y de manejo de los estudios evaluados. Una mayor respuesta fue encontrada en suelos de textura gruesa, sistemas irrigados y/o en cultivos que reciben altas tasas de fertilizante nitrogenado. En suelos alcalinos (pH ≥ 8), el inhibidor de la ureasa NBPT produjo el mayor efecto. Dado que su uso representa un coste adicional para los agricultores, entender las mejores prácticas que permitan maximizar su efectividad es necesario para posteriormente realizar comparaciones efectivas con otras prácticas que incrementen la productividad de los cultivos y el NUE. En base a los resultados del meta-análisis, se seleccionó el NBPT como un inhibidor con gran potencial. Inicialmente desarrollado para reducir la volatilización de amoniaco (NH3), en los últimos años algunos investigadores han demostrado en estudios de campo un efecto mitigador de este inhibidor sobre las pérdidas de N2O provenientes de suelos fertilizados bajo condiciones de baja humedad del suelo. Dada la alta variabilidad de los experimentos de campo, donde la humedad del suelo cambia rápidamente, ha sido imposible entender mecanísticamente el potencial de los inhibidores de la ureasa (UIs) para reducir emisiones de N2O y su dependencia con respecto al porcentaje de poros llenos de agua del suelo (WFPS). Por lo tanto se realizó una incubación en laboratorio con el propósito de evaluar cuál es el principal mecanismo biótico tras las emisiones de N2O cuando se aplican UIs bajo diferentes condiciones de humedad del suelo (40, 60 y 80% WFPS), y para analizar hasta qué punto el WFPS regula el efecto del inhibidor sobre las emisiones de N2O. Un segundo UI (i.e. PPDA) fue utilizado para comparar el efecto del NBPT con el de otro inhibidor de la ureasa disponible comercialmente; esto nos permitió comprobar si el efecto de NBPT es específico de ese inhibidor o no. Las emisiones de N2O al 40% WFPS fueron despreciables, siendo significativamente más bajas que las de todos los tratamientos fertilizantes al 60 y 80% WFPS. Comparado con la urea sin inhibidor, NBPT+U redujo las emisiones de N2O al 60% WFPS pero no tuvo efecto al 80% WFPS. La aplicación de PPDA incrementó significativamente las emisiones con respecto a la urea al 80% WFPS mientras que no se encontró un efecto significativo al 60% WFPS. Al 80% WFPS la desnitrificación fue la principal fuente de las emisiones de N2O en todos los tratamientos mientras que al 60% tanto la nitrificación como la desnitrificación tuvieron un papel relevante. Estos resultados muestran que un correcto manejo del NBPT puede suponer una estrategia efectiva para mitigar las emisiones de N2O. Con el objetivo de trasladar nuestros resultados de los estudios previos a condiciones de campo reales, se desarrolló un experimento en el que se evaluó la efectividad del NBPT para reducir pérdidas de N y aumentar la productividad durante un cultivo de cebada (Hordeum vulgare L.) en secano Mediterráneo. Se determinó el rendimiento del cultivo, las concentraciones de N mineral del suelo, el carbono orgánico disuelto (DOC), el potencial de desnitrificación, y los flujos de NH3, N2O y óxido nítrico (NO). La adición del inhibidor redujo las emisiones de NH3 durante los 30 días posteriores a la aplicación de urea en un 58% y las emisiones netas de N2O y NO durante los 95 días posteriores a la aplicación de urea en un 86 y 88%, respectivamente. El uso de NBPT también incrementó el rendimiento en grano en un 5% y el consumo de N en un 6%, aunque ninguno de estos incrementos fue estadísticamente significativo. Bajo las condiciones experimentales dadas, estos resultados demuestran el potencial del inhibidor de la ureasa NBPT para mitigar las emisiones de NH3, N2O y NO provenientes de suelos arables fertilizados con urea, mediante la ralentización de la hidrólisis de la urea y posterior liberación de menores concentraciones de NH4 + a la capa superior del suelo. El riego por goteo combinado con la aplicación dividida de fertilizante nitrogenado disuelto en el agua de riego (i.e. fertirriego por goteo) se considera normalmente una práctica eficiente para el uso del agua y de los nutrientes. Algunos de los principales factores (WFPS, NH4 + y NO3 -) que regulan las emisiones de GHGs (i.e. N2O, CO2 y CH4) y NO pueden ser fácilmente manipulados por medio del fertirriego por goteo sin que se generen disminuciones del rendimiento. Con ese propósito se evaluaron opciones de manejo para reducir estas emisiones en un experimento de campo durante un cultivo de melón (Cucumis melo L.). Los tratamientos incluyeron distintas frecuencias de riego (semanal/diario) y tipos de fertilizantes nitrogenados (urea/nitrato cálcico) aplicados por fertirriego. Fertirrigar con urea en lugar de nitrato cálcico aumentó las emisiones de N2O y NO por un factor de 2.4 y 2.9, respectivamente (P < 0.005). El riego diario redujo las emisiones de NO un 42% (P < 0.005) pero aumentó las emisiones de CO2 un 21% (P < 0.05) comparado con el riego semanal. Analizando el Poder de Calentamiento global en base al rendimiento así como los factores de emisión del NO, concluimos que el fertirriego semanal con un fertilizante de tipo nítrico es la mejor opción para combinar productividad agronómica con sostenibilidad medioambiental en este tipo de agroecosistemas. Los suelos agrícolas en las áreas semiáridas Mediterráneas se caracterizan por su bajo contenido en materia orgánica y bajos niveles de fertilidad. La aplicación de residuos de cosecha y/o abonos es una alternativa sostenible y eficiente desde el punto de vista económico para superar este problema. Sin embargo, estas prácticas podrían inducir cambios importantes en las emisiones de N2O de estos agroecosistemas, con impactos adicionales en las emisiones de CO2. En este contexto se llevó a cabo un experimento de campo durante un cultivo de cebada (Hordeum vulgare L.) bajo condiciones Mediterráneas para evaluar el efecto de combinar residuos de cosecha de maíz con distintos inputs de fertilizantes nitrogenados (purín de cerdo y/o urea) en estas emisiones. La incorporación de rastrojo de maíz incrementó las emisiones de N2O durante el periodo experimental un 105%. Sin embargo, las emisiones de NO se redujeron significativamente en las parcelas enmendadas con rastrojo. La sustitución parcial de urea por purín de cerdo redujo las emisiones netas de N2O un 46 y 39%, con y sin incorporación de residuo de cosecha respectivamente. Las emisiones netas de NO se redujeron un 38 y un 17% para estos mismos tratamientos. El ratio molar DOC:NO3 - demostró predecir consistentemente las emisiones de N2O y NO. El efecto principal de la interacción entre el fertilizante nitrogenado y el rastrojo de maíz se dio a los 4-6 meses de su aplicación, generando un aumento del N2O y una disminución del NO. La sustitución de urea por purín de cerdo puede considerarse una buena estrategia de manejo dado que el uso de este residuo orgánico redujo las emisiones de óxidos de N. Los pastos de todo el mundo proveen numerosos servicios ecosistémicos pero también suponen una importante fuente de emisión de N2O, especialmente en respuesta a la deposición de N proveniente del ganado mientras pasta. Para explorar el papel de las plantas como mediadoras de estas emisiones, se analizó si las emisiones de N2O dependen de la riqueza en especies herbáceas y/o de la composición específica de especies, en ausencia y presencia de una deposición de orina. Las hipótesis fueron: 1) las emisiones de N2O tienen una relación negativa con la productividad de las plantas; 2) mezclas de cuatro especies generan menores emisiones que monocultivos (dado que su productividad será mayor); 3) las emisiones son menores en combinaciones de especies con distinta morfología radicular y alta biomasa de raíz; y 4) la identidad de las especies clave para reducir el N2O depende de si hay orina o no. Se establecieron monocultivos y mezclas de dos y cuatro especies comunes en pastos con rasgos funcionales divergentes: Lolium perenne L. (Lp), Festuca arundinacea Schreb. (Fa), Phleum pratense L. (Php) y Poa trivialis L. (Pt), y se cuantificaron las emisiones de N2O durante 42 días. No se encontró relación entre la riqueza en especies y las emisiones de N2O. Sin embargo, estas emisiones fueron significativamente menores en ciertas combinaciones de especies. En ausencia de orina, las comunidades de plantas Fa+Php actuaron como un sumidero de N2O, mientras que los monocultivos de estas especies constituyeron una fuente de N2O. Con aplicación de orina la comunidad Lp+Pt redujo (P < 0.001) las emisiones de N2O un 44% comparado con los monocultivos de Lp. Las reducciones de N2O encontradas en ciertas combinaciones de especies pudieron explicarse por una productividad total mayor y por una complementariedad en la morfología radicular. Este estudio muestra que la composición de especies herbáceas es un componente clave que define las emisiones de N2O de los ecosistemas de pasto. La selección de combinaciones de plantas específicas en base a la deposición de N esperada puede, por lo tanto, ser clave para la mitigación de las emisiones de N2O. ABSTRACT Nitrous oxide (N2O) is a potent greenhouse gas (GHG) directly linked to applications of nitrogen (N) fertilizers to agricultural soils. Identifying mitigation strategies for these emissions based on fertilizer management without incurring in yield penalties is of economic and environmental concern. With that aim, this Thesis evaluated: (i) the use of nitrification and urease inhibitors; and (ii) interactions of N fertilizers with (1) water management, (2) crop residues and (3) plant species richness/identity. Meta-analysis, laboratory incubations, greenhouse mesocosm and field experiments were carried out in order to understand and develop effective mitigation strategies. Nitrification and urease inhibitors are proposed as means to reduce N losses, thereby increasing crop nitrogen use efficiency (NUE). However, their effect on crop yield is variable. A meta-analysis was initially conducted to evaluate their effectiveness at increasing NUE and crop productivity. Commonly used nitrification inhibitors (dicyandiamide (DCD) and 3,4-dimethylepyrazole phosphate (DMPP)) and the urease inhibitor N-(n-butyl) thiophosphoric triamide (NBPT) were selected for analysis as they are generally considered the best available options. Our results show that their use can be recommended in order to increase both crop yields and NUE (grand mean increase of 7.5% and 12.9%, respectively). However, their effectiveness was dependent on the environmental and management factors of the studies evaluated. Larger responses were found in coarse-textured soils, irrigated systems and/or crops receiving high nitrogen fertilizer rates. In alkaline soils (pH ≥ 8), the urease inhibitor NBPT produced the largest effect size. Given that their use represents an additional cost for farmers, understanding the best management practices to maximize their effectiveness is paramount to allow effective comparison with other practices that increase crop productivity and NUE. Based on the meta-analysis results, NBPT was identified as a mitigation option with large potential. Urease inhibitors (UIs) have shown to promote high N use efficiency by reducing ammonia (NH3) volatilization. In the last few years, however, some field researches have shown an effective mitigation of UIs over N2O losses from fertilized soils under conditions of low soil moisture. Given the inherent high variability of field experiments where soil moisture content changes rapidly, it has been impossible to mechanistically understand the potential of UIs to reduce N2O emissions and its dependency on the soil water-filled pore space (WFPS). An incubation experiment was carried out aiming to assess what is the main biotic mechanism behind N2O emission when UIs are applied under different soil moisture conditions (40, 60 and 80% WFPS), and to analyze to what extent the soil WFPS regulates the effect of the inhibitor over N2O emissions. A second UI (i.e. PPDA) was also used aiming to compare the effect of NBPT with that of another commercially available urease inhibitor; this allowed us to see if the effect of NBPT was inhibitor-specific or not. The N2O emissions at 40% WFPS were almost negligible, being significantly lower from all fertilized treatments than that produced at 60 and 80% WFPS. Compared to urea alone, NBPT+U reduced the N2O emissions at 60% WFPS but had no effect at 80% WFPS. The application of PPDA significantly increased the emissions with respect to U at 80% WFPS whereas no significant effect was found at 60% WFPS. At 80% WFPS denitrification was the main source of N2O emissions for all treatments. Both nitrification and denitrification had a determinant role on these emissions at 60% WFPS. These results suggest that adequate management of the UI NBPT can provide, under certain soil conditions, an opportunity for N2O mitigation. We translated our previous results to realistic field conditions by means of a field experiment with a barley crop (Hordeum vulgare L.) under rainfed Mediterranean conditions in which we evaluated the effectiveness of NBPT to reduce N losses and increase crop yields. Crop yield, soil mineral N concentrations, dissolved organic carbon (DOC), denitrification potential, NH3, N2O and nitric oxide (NO) fluxes were measured during the growing season. The inclusion of the inhibitor reduced NH3 emissions in the 30 d following urea application by 58% and net N2O and NO emissions in the 95 d following urea application by 86 and 88%, respectively. NBPT addition also increased grain yield by 5% and N uptake by 6%, although neither increase was statistically significant. Under the experimental conditions presented here, these results demonstrate the potential of the urease inhibitor NBPT in abating NH3, N2O and NO emissions from arable soils fertilized with urea, slowing urea hydrolysis and releasing lower concentrations of NH4 + to the upper soil layer. Drip irrigation combined with split application of N fertilizer dissolved in the irrigation water (i.e. drip fertigation) is commonly considered best management practice for water and nutrient efficiency. Some of the main factors (WFPS, NH4 + and NO3 -) regulating the emissions of GHGs (i.e. N2O, carbon dioxide (CO2) and methane (CH4)) and NO can easily be manipulated by drip fertigation without yield penalties. In this study, we tested management options to reduce these emissions in a field experiment with a melon (Cucumis melo L.) crop. Treatments included drip irrigation frequency (weekly/daily) and type of N fertilizer (urea/calcium nitrate) applied by fertigation. Crop yield, environmental parameters, soil mineral N concentrations, N2O, NO, CH4, and CO2 fluxes were measured during the growing season. Fertigation with urea instead of calcium nitrate increased N2O and NO emissions by a factor of 2.4 and 2.9, respectively (P < 0.005). Daily irrigation reduced NO emissions by 42% (P < 0.005) but increased CO2 emissions by 21% (P < 0.05) compared with weekly irrigation. Based on yield-scaled Global Warming Potential as well as NO emission factors, we conclude that weekly fertigation with a NO3 --based fertilizer is the best option to combine agronomic productivity with environmental sustainability. Agricultural soils in semiarid Mediterranean areas are characterized by low organic matter contents and low fertility levels. Application of crop residues and/or manures as amendments is a cost-effective and sustainable alternative to overcome this problem. However, these management practices may induce important changes in the nitrogen oxide emissions from these agroecosystems, with additional impacts on CO2 emissions. In this context, a field experiment was carried out with a barley (Hordeum vulgare L.) crop under Mediterranean conditions to evaluate the effect of combining maize (Zea mays L.) residues and N fertilizer inputs (organic and/or mineral) on these emissions. Crop yield and N uptake, soil mineral N concentrations, dissolved organic carbon (DOC), denitrification capacity, N2O, NO and CO2 fluxes were measured during the growing season. The incorporation of maize stover increased N2O emissions during the experimental period by c. 105 %. Conversely, NO emissions were significantly reduced in the plots amended with crop residues. The partial substitution of urea by pig slurry reduced net N2O emissions by 46 and 39 %, with and without the incorporation of crop residues respectively. Net emissions of NO were reduced 38 and 17 % for the same treatments. Molar DOC:NO3 - ratio was found to be a robust predictor of N2O and NO fluxes. The main effect of the interaction between crop residue and N fertilizer application occurred in the medium term (4-6 month after application), enhancing N2O emissions and decreasing NO emissions as consequence of residue incorporation. The substitution of urea by pig slurry can be considered a good management strategy since N2O and NO emissions were reduced by the use of the organic residue. Grassland ecosystems worldwide provide many important ecosystem services but they also function as a major source of N2O, especially in response to N deposition by grazing animals. In order to explore the role of plants as mediators of these emissions, we tested whether and how N2O emissions are dependent on grass species richness and/or specific grass species composition in the absence and presence of urine deposition. We hypothesized that: 1) N2O emissions relate negatively to plant productivity; 2) four-species mixtures have lower emissions than monocultures (as they are expected to be more productive); 3) emissions are lowest in combinations of species with diverging root morphology and high root biomass; and 4) the identity of the key species that reduce N2O emissions is dependent on urine deposition. We established monocultures and two- and four-species mixtures of common grass species with diverging functional traits: Lolium perenne L. (Lp), Festuca arundinacea Schreb. (Fa), Phleum pratense L. (Php) and Poa trivialis L. (Pt), and quantified N2O emissions for 42 days. We found no relation between plant species richness and N2O emissions. However, N2O emissions were significantly reduced in specific plant species combinations. In the absence of urine, plant communities of Fa+Php acted as a sink for N2O, whereas the monocultures of these species constituted a N2O source. With urine application Lp+Pt plant communities reduced (P < 0.001) N2O emissions by 44% compared to monocultures of Lp. Reductions in N2O emissions by species mixtures could be explained by total biomass productivity and by complementarity in root morphology. Our study shows that plant species composition is a key component underlying N2O emissions from grassland ecosystems. Selection of specific grass species combinations in the context of the expected nitrogen deposition regimes may therefore provide a key management practice for mitigation of N2O emissions.