Evaluación del estado de eutrofización del mar Alborán mediante el empleo combinado de imágenes de satélite y de muestreos in situ

La eutrofización marina es un problema que afecta a los mares europeos y particularmente a sus aguas costeras. Se trata del enriquecimiento anómalo en nutrientes de las aguas marinas, generalmente compuestos del nitrógeno y fósforo aportados por la actividad del ser humano, y que tiene como resultado consecuencias nocivas para la calidad de las aguas y la biodiversidad. La Directiva Marco de las Estrategias Marinas, que entró en vigor en 2010, recoge esta problemática y emplaza a los estados miembros para su evaluación y en su caso para la remediación de sus efectos nocivos identificando el origen de los aportes de nutrientes. Esta tarea requiere metodologías y procedimientos operativos que permitan ser implementados de forma coordinada por los estados miembros a nivel regional. En el primer capítulo de esta tesis se presenta una metodología para realizar la zonación del norte del mar Alborán a partir de imágenes de satélite de clorofila a tal que permite delimitar las áreas con características de productividad diferenciadas que pueden ser propuestas como unidades de gestión de la eutrofización y que se puedan emplear tanto en el diseño de los programas de seguimiento como en el aprovechamiento de los datos oceanográficos medidos in situ. En este capítulo se describe la metodología analítica utilizada, que está basada en la aplicación del análisis clúster de las k-medias a las imágenes de satélite de clorofila, así como su validez a partir del análisis de las series temporales de datos tomados in situ. El segundo capítulo se hace una evaluación de los indicadores de la eutrofización en una zona reducida de Alborán, donde existen multitud de datos oceanográficos, meteorológicos y ambientales. Para llevarla a cabo, se adaptó la metodología empleada en el capítulo 1 a la región ECOMALAGA. Una vez realizada la zonación, se agregaron los datos oceanográficos, meteorológicos y ambientales potencialmente relacionados con la eutrofización en cada área, y posteriormente se evaluaron las diferencias estadísticas a lo largo del ciclo estacional y entre las diferentes zonas. Con esta finalidad, se estiman las tendencias temporales de las variables ambientales en cada zona. A partir de los resultados obtenidos se infirió qué variables y/o mecanismos podrían estar influyendo sobre la concentración superficial de la clorofila a. En el tercer capítulo se ensayaron modelos aditivos generalizados (GAM) con el fin de identificar las variables más importantes que afectan a los indicadores de la eutrofización. Como variable respuesta del modelo se usó la clorofila a, pues se trata del indicador directo de la eutrofización más empleado. Las variables explicativas se componen de variables oceanográficas, meteorológicas y ambientales. En el cuarto capítulo se desarrolla un algoritmo regional para el mar de Alborán que permite obtener valores de clorofila a a partir de imágenes de satélite más ajustados a los valores que proporcionan los algoritmos disponibles que la sobreestiman considerablemente. En la discusión final y conclusiones se hace énfasis en el enfoque práctico de esta tesis doctoral, detallando la potencialidad de la metodología presentada para la evaluación de la eutrofización. Para esto, se detallan los resultados de la evaluación obtenidos para el mar Alborán empleando dicha metodología, definiendo su estado actual y las tendencias registradas, así como las causas de los problemas encontrados. Finalmente se evalúan y proponen posibles medidas para su remediación y control.

Synthesis of active Belite-Alite-Ye'elimite clinker (BAY)

Ordinary Portland cement (OPC) is an environmentally contentious material, as for every ton of OPC produced, on average, 0.97 tons of CO2 are released. Ye'elimite-rich cements are considered as eco-cements because their manufacturing process releases less CO2 into the atmosphere than OPC; this is due to the low calcite demand. Belite-Alite-Ye’elimite (BAY) cements are promising eco-friendly building materials as OPC substitutes at a large scale. The reaction of alite and ye´elimite with water should develop cements with high mechanical strengths at early ages, while belite will contribute to later curing times. However, they develop lower mechanical strengths at early-medium ages than OPC. It is known that the presence of different polymorphs of ye'elimite and belite affects the hydration due to the different reactivity of those phases. Thus, a solution to this problem may be well the activation of BAY clinkers by preparing them with 'H-belite and pseudo-cubic-ye'elimite, jointly with alite. The aim of this work is the preparation and characterization of active-BAY clinkers which contain high percentages of coexisting 'H-belite and pseudo-cubic-ye'elimite, jointly with alite to develop, in a future step, comparable mechanical strengths to OPC. The parameters evolved in the preparation of the clinker have been optimized, including the selection of raw materials (mineralizers and activators) and clinkering conditions. Finally, the clinker was characterized through laboratory X-ray powder diffraction, in combination with the Rietveld methodology, and scanning electron microscopy.

Synthesis and behavior of Belite-Alite-Ye’elimite (BAY) cement

Ye’elimite based cements have been studied since 70’s years in China, due to the irrelevant characteristics from a hydraulic and environmental point of view. One of them is the reduced fuel consumption, related to the lower temperature reaction required for this kind of cement production as compared to Ordinary Portland Cement (OPC), another characteristic is the reduced requirement of carbonates as a typical raw material, compared to OPC, with the consequent reduction in CO2 releases (~22%)from combustion. Thus, Belite-Ye’elimite-Ferrite (BYF) cements have been developed as potential OPC substitutes. BYF cements contain belite as main phase (>50 wt%) and ye´elimite as the second content phase (~30 wt%). However, an important technological problem is associated to them, related to the low mechanical strengths developed at intermediate hydration ages (3, 7 and 28 days). One of the proposed solutions to this problem is the activation of BYF clinkers by preparing clinkers with high percentage of coexisting alite and ye'elimite. These clinkers are known Belite-Alite-Ye’elimite (BAY) cements. Their manufacture would produce ~15% less CO2 than OPC. Alite is the main component of OPC and is responsible for early mechanical strengths. The reaction of alite and ye´elimite with water will develop cements with high mechanical strengths at early ages, while belite will contribute to later curing times. Moreover, the high alkalinity of BAY cement pastes/mortars/concretes may facilitate the use of supplementary cementitious materials with pozzolanic activity which also contributes to decrease the CO2 footprint of these ecocements. The main objective of this work was the design and optimization of all the parameters evolved in the preparation of a BAY eco-cement that develop higher mechanical strengths than BYF cements. These parameters include the selection of the raw materials (lime, gypsum, kaolin and sand), milling, clinkering conditions (temperature, and holding time), and clinker characterization The addition of fly ash has also been studied. All BAY clinker and pastes (at different hydration ages) were mineralogically characterized through laboratory X-ray powder diffraction (LXRPD) in combination with the Rietveld methodology to obtain the full phase assemblage including Amorphous and Crystalline non-quantified, ACn, contents. The pastes were also characterized through rheological measurements, thermal analyses (TA), scanning electronic microscopy (SEM) and nuclear magnetic resonance (NMR). The compressive strengths were also measured at different hydration times and compared to BYF.

In-situ Molibdenum X-ray powder diffraction study of the early hydration of cementitious systems on a humidity chamber

The durability of cement-based construction materials depends on the environmental conditions during their service life. A further factor is the microstructure of the cement bulk, established by formation of cement hydrates. The development of the phases and microstructure under given conditions is responsible of the high strength of cementitious materials. The investigation on the early hydration behavior of cements and cementing systems has been for a long time a very important area of research: understanding the chemical reactions that lead to hardening is fundamental for the prediction of performances and durability of the materials. The production of 1 ton of Ordinary Portland Cement, OPC, releases into the atmosphere ~0.97 tons of CO2. This implies that the overall CO2 emissions from the cement industry are 6% of all anthropogenic carbon dioxide. An alternative to reduce the CO2 footprint consists on the development of eco-cements composed by less calcite demanding phases, such as belite and ye'elimite. That is the case of Belite-Ye’elimite cements (BY). Since the reactivity of belite is not quick enough, these materials develop low mechanical strengths at intermediate hydration ages. A possible solution to this problem goes through the production of cements which jointly contain alite with the two previously mentioned phases, named as Belite-Alite-Ye’elimite (BAY) cements. The reaction of alite and ye'elimite with water will develop cements with high mechanical strengths at early ages, while belite will contribute to later values. The final goal is to understand the hydration mechanisms of a variety of cementing systems (OPC, BAY and pure phases) as a function of water content, superplasticizer additives and type and content of sulfate source. In order to do so, in-situ laboratory humidity chambers with Molybdenum X-ray Powder diffraction are employed. In the first 2h of hydration, reaction degree (α) of ye'elimite had been decreased for superplasticizer.

De necesidad funcional al uso lúdico: recuperación del "Caminito del Rey" en el complejo hidroeléctrico de Guadalhorce (Málaga, España)

La llegada del ff.cc. de la línea Málaga-Córdoba a la localidad de Álora en 1865 abrió nuevas perspectivas de desarrollo económico, que continuó a partir de 1903 con la construcción de embalses para la producción de energía eléctrica. El ingeniero Rafael Benjumea construyó el salto El Chorro y Guadalteba a ambos lados del impresionante desfiladero de Los Gaitanes, y una estrecha pasarela a gran altura para comunicarlos. Su restauración ha abierto nuevas posibilidades turísticas para esta zona basadas en el paisaje y el turismo industrial.

Applications of synchrotron x-ray powder diffraction in hydrated cements: high-resolution and high-pressure studies

The main aim of this study is to apply synchrotron radiation techniques for the study of hydrated cement pastes. In particular, the tetracalcium aluminoferrite phase, C4AF in cement nomenclature, is the major iron-containing phase in Ordinary Portland Cement (OPC) and in iron rich belite calcium sulfoaluminate cements. In a first study, the hydration mechanism of pure tetracalcium aluminoferrite phase with water-to-solid ratio of 1.0 has been investigated by HR-SXRPD (high resolution synchrotron X-ray powder diffraction). C4AF in the presence of water hydrates to form mainly an iron-containing hydrogarnet-type (katoite) phase, C3A0.84F0.16H6, as single crystalline phase. Its crystal structure and stoichiometry were determined by the Rietveld method and the final disagreement factors were RWP=8.1% and RF=4.8% [1]. As the iron content in the product is lower than that in C4AF, it is assumed that part of the iron also goes to an amorphous iron rich gel, like the hydrated alumina-type gel, as hydration proceeds. Further results from the high-resolution study will be discussed. In a second study, the behavior of pure and iron-containing katoites (C3AH6 and C3A0.84F0.16H6) under pressure have been analyzed by SXRPD using a diamond anvil cell (DAC) and then their bulk moduli were determined. The role of the pressure transmitting medium (PTM) has also been studied. In this case, silicone oil as well as methanol/ethanol mixtures have been used as PTM. Some “new peaks” were detected in the pattern for C3A0.84F0.16H6 as pressure increases, when using ethanol/methanol as PTM. These new peaks were still present at ambient pressure after releasing the applied pressure. They may correspond to crystalline nordstrandite or doyleite from the crystallization of amorphous aluminium hydroxide. The results from the high-pressure study will also be discussed.