Cultural oak landscapes as green infrastructure for human well-being

Human and nature interactions have been the ancestral normative model to provide and secure livelihoods worldwide. Hence, humans have been coevolving in an intrinsic relation with the natural system until medieval times. The mentioned interactions formed the so-called cultural landscapes as a result of human gradual re-organization and adaptation of the biophysical system to adapt better to changing societal demands. Concerned to balance sustainable development of landscapes among its social, economic and environmental dimensions, as well as aware of the important role of landscapes for individual and social well-being through their protection, management and planning, the European Landscape Convention emerged. The cultural dimension of landscapes has proven difficult to measure and thus commonly neglected in ecosystem services (ES) research. To tackle this knowledge gap, I first reviewed methods and tools to fully capture cultural ecosystem services in landscapes, to focus thereafter on the diagnosis of the cultural oak landscape in Östergötland (Sweden). I identified and analyzed the diversity of ES important for stakeholders at local and regional levels that represent different societal sectors. The private sector locally emphasized provisioning ES, whereas the civil and public sectors highlighted the importance of cultural services in terms of recreational values and landscape beauty. Supporting services were considered only in relation to biodiversity, especially species and habitats linked to old oaks. Hotspot of ES were identified and discussed in terms of green infrastructures for human well-being. Traditional farming practices are in a steady regression which entails greater uncertainty for the long term survival of such systems and associated diversity of delivered services and values. Solutions, including adaptations of modern farming techniques to better mimic the traditional ones are urgently needed, as well as the generation of additional income through alternative rural development initiatives such as tourism and recreation. Complex realities demand multi-disciplinary methods and approaches to find viable ground-based solutions. We suggest holistic research methods, hands on with stakeholders, i.e. transdisciplinary research, to satisfy the increasingly complex needs, improved understanding of conservation objectives and demands of a changing society

Metastability and Avalanches in a Nonequilibrium Ferromagnetic System

We present preliminary results on the metastable behavior of a nonequilibrium ferromagnetic system. The metastable state mean lifetime is a non-monotonous function of temperature; it shows a maximum at certain non-zero temperature which depends on the strengh of the nonequilibrium perturbation. This is in contrast with the equilibrium case in which lifetime increases monotonously as the temperature is decreasesed. We also report on avalanches during the decay from the metastable state. Assuming both free boundaries and nonequilibrium impurities, the avalanches exhibit power-law size and lifetime distributions. Such scale free behavior is very sensible. The chances are that our observations may be observable in real (i.e. impure) ferromagnetic nanoparticles.Comment: 6 pages, 4 figures, to be published in 2002 Granada Seminar Proceeding

Test of the Additivity Principle for Current Fluctuations in a Model of Heat Conduction

The additivity principle allows to compute the current distribution in many one-dimensional (1D) nonequilibrium systems. Using simulations, we confirm this conjecture in the 1D Kipnis-Marchioro-Presutti model of heat conduction for a wide current interval. The current distribution shows both Gaussian and non-Gaussian regimes, and obeys the Gallavotti-Cohen fluctuation theorem. We verify the existence of a well-defined temperature profile associated to a given current fluctuation. This profile is independent of the sign of the current, and this symmetry extends to higher-order profiles and spatial correlations. We also show that finite-time joint fluctuations of the current and the profile are described by the additivity functional. These results suggest the additivity hypothesis as a general and powerful tool to compute current distributions in many nonequilibrium systems.Comment: 4 pages, 4 figure

Molecular Water Oxidation Catalysts Based on Copper and Nickel Complexes

Aquesta Tesi Doctoral es centra en l’estudi de catalitzadors moleculars per a l’oxidació d’aigua basats en coure i níquel, ja que la seva gran abundància i baix cost els fa potencials candidats pel seu ús en sistemes catalítics. Tot i així, avui en dia hi ha una important mancança d’informació respecte als seus mecanismes de reacció i els factors que influeixen la seva activitat. Per això, en primer lloc, es desenvolupen nous catalitzadors moleculars basats en el coure com a centre metàl·lic. L’estudi mecanístic d’aquests catalitzadors revela l’important rol que té l’oxidació del lligand en el cicle catalític a l’hora de controlar el sobre-potencial de la reacció. Al mateix temps, en col·laboració amb el grup del Professor Maseras (ICIQ) es descobreix un nou mecanisme per a la formació de l’enllaç oxigen-oxigen que opera en diferents tipus catalitzadors de coure. Aquest nou mecanisme sense precedents permet redefinir l’escenari mecanístic per a l’oxidació d’aigua. Posteriorment, es realitza el disseny de nous lligands amb diferents propietats redox que permeten estudiar factors que influeixen en l’activitat i el mecanisme de reacció. Això proporciona informació rellevant per al disseny de nous catalitzadors més actius, estables i eficients. També s’aborda la immobilització dels catalitzadors desenvolupats sobre els elèctrodes basats en grafè. D’aquesta manera es descobreix el paper essencial que té la deslocalització d’electrons en els orbitals π, que permet incrementar la cinètica de la reacció per més de dues ordres de magnitud. Finalment, el coneixement generat en coure s’intenta expandir per a la seva aplicació en els catalitzadors de níquel. Això permet estudiar el caràcter làbil dels complexos de níquel en medis bàsics, que determina la presència de dos mecanismes d’operació basats en espècies moleculars i òxids de níquel respectivament.Esta Tesis Doctoral se centra en el estudio de catalizadores moleculares para la oxidación de agua basados en cobre y níquel, ya que su gran abundancia y su bajo coste los hace potenciales candidatos para su uso en sistemas catalíticos. A pesar de esto, hoy en día hay una importante carencia de información con respecto a sus mecanismos de reacción y los factores que determinan su actividad. Por ello, en primer lugar, se desarrollan nuevos catalizadores moleculares basados en cobre como centro metálico. El estudio mecanístico de dichos catalizadores revela el importante rol que tiene la oxidación del ligando en el ciclo catalítico a la hora de controlar el sobre-potencial de la reacción. Al mismo tiempo, en colaboración con el grupo del Profesor Maseras (ICIQ) se descubre un nuevo mecanismo para la formación del enlace oxígeno-oxígeno que opera en diferentes tipos de catalizadores de cobre. Este nuevo mecanismo sin precedentes permite redefinir el escenario mecanístico para la oxidación de agua. Posteriormente, se realiza el diseño de nuevos ligandos con diferentes propiedades redox que permiten estudiar los factores que influyen en la actividad y el mecanismo de reacción. Esto proporciona información relevante para el diseño de nuevos catalizadores más activos, estables y eficientes. También se aborda la inmovilización de los catalizadores desarrollados sobre electrodos basados en grafeno. De esta forma se descubre el papel esencial que tiene la deslocalización de electrones en orbitales π, que permite incrementar la cinética de reacción por más de dos órdenes de magnitud. Finalmente, el conocimiento generado en cobre se intenta expandir para su aplicación en catalizadores de níquel. Esto permite estudiar el carácter lábil de los complejos de níquel en medios básicos, que determina la presencia de dos mecanismos de operación basados en especies moleculares y óxidos de níquel respectivamente.This Doctoral Thesis focuses on the study of molecular catalysts for water oxidation based on copper and nickel since their high abundance and inexpensive character make them potential candidates for their use in catalytic systems. Despite that, there is a current lack of information regarding their reaction mechanism and the factors that determine their activity. Therefore, we first develop new molecular catalysts based on copper as metal center. Their mechanistic study reveals the essential role that the ligand oxidation has in the catalytic cycle as tool to control the reaction overpotential. In collaboration with Prof. Maseras group (ICIQ) a new mechanism for the oxygen-oxygen bond formation is found to operate in different copper catalysts. This unprecedented mechanism allows us to redefine the mechanistic scenario in water oxidation. Later on, the design of new ligands with different redox properties is addressed. That allows to study the factors that have influence on the activity and reaction mechanism and provide valuable information for the design of more active, stable and efficient new catalysts. Moreover, the immobilization of the molecular catalyst on the surface of graphene-based electrodes is also studied. We discover the essential role of the π-delocalization in increasing the reaction kinetic by more than two orders of magnitude. Finally, the knowledge developed with copper complexes is applied in nickel catalysis. This allows to study the labile character of nickel complexes in basic media that determine the presence of two different operating mechanism based on molecular species and nickel oxides respectively