Generalised integrable λ- and η-deformations and their relation

We construct two-parameter families of integrable λ -deformations of two-dimensional field theories. These interpolate between a CFT (a WZW/gauged WZW model) and the non-Abelian T-dual of a principal chiral model on a group/symmetric coset space. In examples based on the SU(2) WZW model and the SU(2)/U(1) exact coset CFT, we show that these deformations are related to bi-Yang–Baxter generalisations of η-deformations via Poisson–Lie T-duality and analytic continuation. We illustrate the quantum behaviour of our models under RG flow. As a byproduct we demonstrate that the bi-Yang–Baxter σ-model for a general group is one-loop renormalisable.

Lying, Integrity, and Cooperation

While talk is cheap to some, it is expensive to others for whom moral considerations come into play. We employ a simple two-stage modified prisoner's dilemma game where integrity is endowed on a continuum to analyze when agents will lie in random economic interactions. If there is sufficient integrity in the population, all agents make a promise in the first stage to cooperate in the second. Some agents always lie, some always tell the truth, and some behave conditionally. Enhanced cooperation is a byproduct of integrity.

The experience and meaning of injury among migrant farmworkers from Starr County, Texas

Occupational injuries suffered by migrant farmworkers in the United States continue to be a significant byproduct of the hazards of the agricultural work sector. Although the fields of study involving occupational health and safety have helped to further an understanding of the importance of injury prevention in the workplace, farmworkers have typically not been the beneficiaries of significant improvement in working conditions; similarly, public health policies have generally not been successful in significantly improving their protection. The primary objective of this research was to examine more closely, through in-depth interviews, the underlying reasons attributed by migrant farmworkers to their having suffered occupational injuries. By re-contacting and re-interviewing migrant farmworkers who had reported injuries in a study entitled A Cohort Study of Injuries in Migrant Farmworker Families in South Texas, the current research study employed qualitative research methods and determined several reasons that may help to explain why this specific group has suffered injuries and may not have reported such injuries, as well as to consider what their experiences may say about injury prevention within the context of public health.^

Delayed Thrombus Resolution and Fibroproliferative Vascular Wound Healing From Deficiency of Type III Collagen: a Paradoxical Mechanism for Tissue Fragility

Vascular Ehlers-Danlos syndrome is a heritable disease of connective tissue caused by mutations in COL3A1, conferring a tissue deficiency of type III collagen. Cutaneous wounds heal poorly in these patients, and they are susceptible to spontaneous and catastrophic rupture of expansible hollow organs like the gut, uterus, and medium-sized to large arteries, which leads to premature death. Although the predisposition for organ rupture is often attributed to inherent tissue fragility, investigation of arteries from a haploinsufficient Col3a1 mouse model (Col3a1+/-) demonstrates that mutant arteries withstand even supraphysiologic pressures comparably to wild-type vessels. We hypothesize that injury that elicits occlusive thrombi instead unmasks defective thrombus resolution resulting from impaired production of type III collagen, which causes deranged remodeling of matrix, persistent inflammation, and dysregulated behavior by resident myofibroblasts, culminating in the development of penetrating neovascular channels that disrupt the mechanical integrity of the arterial wall. Vascular injury and thrombus formation following ligation of the carotid artery reveals an abnormal persistence and elevated burden of occlusive thrombi at 21 post-operative days in vessels from Col3a1+/- mice, as opposed to near complete resolution and formation of a patent and mature neointima in wild-type mice. At only 14 days, both groups harbor comparable burdens of resolving thrombi, but wild-type mice increase production of type III collagen in actively resolving tissues, while mutant mice do not. Rather, thrombi in mutant mice contain higher burdens of macrophages and proliferative myofibroblasts, which persist through 21 days while wild-type thrombi, inflammatory cells, and proliferation all regress. At the same time that increased macrophage burdens were observed at 14 and 21 days post ligation, the medial layer of mutant arterial walls concurrently harbored a significantly higher incidence of penetrating neovessels compared with those in wild-type mice. To assess whether limited type III collagen production alters myofibroblast behavior, fibroblasts from vEDS patients with COL3A1 missense mutations were seeded into three-dimensional fibrin gel constructs and stimulated with transforming growth factor-β1 to initiate myofibroblast differentiation. Although early signaling events occur similarly in all cell lines, late extracellular matrix- and mechanically-regulated events like transcriptional upregulation of type I and type III collagen secretion are delayed in mutant cultures, while transcription of genes encoding intracellular contractile machinery is increased. Sophisticated imaging of collagen synthesized de novo by resident myofibroblasts visualizes complex matrix reorganization by control cells but only meager remodeling by COL3A1 mutant cells, concordant with their compensatory contraction to maintain tension in the matrix. Finally, administration of immunosuppressive rapamycin to mice following carotid ligation sufficiently halts the initial inflammatory phase of thrombus resolution and fully prevents both myofibroblast migration into the thrombus and the differential development of neovessels between mutant and wild-type mice, suggesting that pathological defects in mutant arteries develop secondarily to myofibroblast dysfunction and chronic inflammatory stimulation, rather than as a manifestation of tissue fragility. Together these data establish evidence that pathological defects in the vessel wall architecture develop in mutant arteries as sequelae to abnormal healing and remodeling responses activated by arterial injury. Thus, these data support the hypothesis that events threatening the integrity of type III collagen-deficient vessels develop not as a result of inherent tissue weakness and fragility at baseline but instead as an episodic byproduct of abnormally persistent granulation tissue and fibroproliferative intravascular remodeling.

Los elementos mixtos en la teoría de elementos de contorno

En este trabajo se expone la formulación del B.I.E.M. (en problemas de potencial)con elementos mixtos, que representan una interpolación lineal en la función de campo y constante en su derivada. El objetivo primordial de dicha formulación, es el soslayar los problemas que se presentan con los planteamientos anteriores, cuando existen puntos singulares. Los ejemplos que se incluyen, resueltos mediante un programa desarrollado en un miniordenador, confirman que el método propuesto consigue mejores resultados, sin ninguna complicación adicional sobre la formulación general, y con un ahorro significativo en cuanto al número de incógnitas y ecuaciones que se han de resolver = In this paper the mixed B.I.E.M. for bidimensional potential problems is presented. The interpolation of the field variable is done by piecewise constant one. The main idea is to swep out the solution the parasitic disturbances introduced near singular points by a finite value although an important byproduct is the possibility of conexion with domain methods, as F.E.M., in which the same kind of interpolation is worked. Results are very good, as shown by the exemples, and also interesting is the reduction in computer time comparatively to the classical B.l.E.M approach.

Derivación deductiva de programas funcionales con patrones

Una de las dificultades principales en el desarrollo de software es la ausencia de un marco conceptual adecuado para su estudio. Una propuesta la constituye el modelo transformativo, que entiende el desarrollo de software como un proceso iterativo de transformación de especificaciones: se parte de una especificación inicial que va transformándose sucesivamente hasta obtener una especificación final que se toma como programa. Este modelo básico puede llevarse a la práctica de varias maneras. En concreto, la aproximación deductiva toma una sentencia lógica como especificación inicial y su proceso transformador consiste en la demostración de la sentencia; como producto secundario de la demostración se deriva un programa que satisface la especificación inicial. La tesis desarrolla un método deductivo para la derivación de programas funcionales con patrones, escritos en un lenguaje similar a Hope. El método utiliza una lógica multigénero, cuya relación con el lenguaje de programación es estudiada. También se identifican los esquemas de demostración necesarios para la derivación de funciones con patrones, basados en la demostración independiente de varias subsentencias. Cada subsentencia proporciona una subespecificación de una ecuación del futuro programa a derivar. Nuestro método deductivo está inspirado en uno previo de Zohar Manna y Richard Waldinger, conocido como el cuadro deductivo, que deriva programas en un lenguaje similar a Lisp. El nuevo método es una modificación del cuadro de estos autores, que incorpora géneros y permite demostrar una especificación mediante varios cuadros. Cada cuadro demuestra una subespecificación y por tanto deriva una ecuación del programa. Se prevén mecanismos para que los programas derivados puedan contener definiciones locales con patrones y variables anónimas y sinónimas y para que las funciones auxiliares derivadas no usen variables de las funciones principales. La tesis se completa con varios ejemplos de aplicación, un mecanismo que independentiza el método del lenguaje de programación y un prototipo de entorno interactivo de derivación deductiva. Categorías y descriptores de materia CR D.l.l [Técnicas de programación]: Programación funcional; D.2.10 [Ingeniería de software]: Diseño - métodos; F.3.1 [Lógica y significado de los programas]: Especificación, verificación y razonamiento sobre programas - lógica de programas; F.3.3 [Lógica y significado de los programas]: Estudios de construcciones de programas - construcciones funcionales; esquemas de programa y de recursion; 1.2.2 [Inteligencia artificial]: Programación automática - síntesis de programas; 1.2.3 [Inteligencia artificial]: Deducción y demostración de teoremas]: extracción de respuesta/razón; inducción matemática. Términos generales Programación funcional, síntesis de programas, demostración de teoremas. Otras palabras claves y expresiones Funciones con patrones, cuadro deductivo, especificación parcial, inducción estructural, teorema de descomposición.---ABSTRACT---One of the main difficulties in software development is the lack of an adequate conceptual framework of study. The transformational model is one such proposal that conceives software development as an iterative process of specifications transformation: an initial specification is developed and successively transformed until a final specification is obtained and taken as a program. This basic model can be implemented in several ways. The deductive approach takes a logical sentence as the initial specification and its proof constitutes the transformational process; as a byproduct of the proof, a program which satisfies the initial specification is derived. In the thesis, a deductive method for the derivation of Hope-like functional programs with patterns is developed. The method uses a many-sorted logic, whose relation to the programming language is studied. Also the proof schemes necessary for the derivation of functional programs with patterns, based on the independent proof of several subsentences, are identified. Each subsentence provides a subspecification of one equation of the future program to be derived. Our deductive method is inspired on a previous one by Zohar Manna and Richard Waldinger, known as the deductive tableau, which derives Lisp-like programs. The new method incorporates sorts in the tableau and allows to prove a sentence with several tableaux. Each tableau proves a subspecification and therefore derives an equation of the program. Mechanisms are included to allow the derived programs to contain local definitions with patterns and anonymous and synonymous variables; also, the derived auxiliary functions cannot reference parameters of their main functions. The thesis is completed with several application examples, i mechanism to make the method independent from the programming language and an interactive environment prototype for deductive derivation. CR categories and subject descriptors D.l.l [Programming techniques]: Functional programming; D.2.10 [Software engineering]: Design - methodologies; F.3.1 [Logics and meanings of programa]: Specifying and verifying and reasoning about programs - logics of programs; F.3.3 [Logics and meanings of programs]: Studies of program constructs - functional constructs; program and recursion schemes; 1.2.2 [Artificial intelligence]: Automatic programming - program synthesis; 1.2.3 [Artificial intelligence]: Deduction and theorem proving - answer/reason extraction; mathematical induction. General tenas Functional programming, program synthesis, theorem proving. Additional key words and phrases Functions with patterns, deductive tableau, structural induction, partial specification, descomposition theorem.

Capacidad y comportamiento de la adsorción de fenol en caolines naturales y modificados

En la actualidad las industrias químicas, farmacéuticas y clínicas, originan contaminantes en aguas superficiales, aguas subterráneas y suelos de nuestro país, como es el caso del fenol, contaminante orgánico común y altamente dañino para los organismos, incluso a bajas concentraciones. Existen en el mercado diferentes metodologías para minimizar la contaminación pero muchos de estos procesos tienen un alto coste, generación de contaminantes, etc. La adsorción de contaminantes por medio de arcillas es un método ampliamente utilizado, encontrándose eficaz y económico. Pero la dificultad de adsorber un contaminante orgánico como el fenol motiva la creación de un material llamado organoarcillas. Las organoarcillas son arcillas modificadas con un surfactante, a su vez, los surfactantes son moléculas orgánicas que confieren a la superficie de la arcilla carga catiónica en lugar de aniónica, haciendo más fácil la adsorción de fenol. Para esta tesis se ha elegido el caolín como material adsorbente, fácilmente disponible y relativamente de bajo coste. Se ha trabajado con: arenas de caolín, material directo de la extracción, y caolín lavado, originado del proceso de lavado de las arenas de caolín. Ambos grupos se diferencian fundamentalmente por su contenido en cuarzo, ampliamente mayor en las arenas de caolín. Con el objetivo de desarrollar un material a partir del caolín y arenas de éste con capacidad de retención de contaminates, en concreto, fenol, se procedió a modificar los materiales de partida mediante tratamientos térmicos, mecánicos y/o químicos, dando lugar a compuestos con mayor superficie química reactiva. Para ello se sometió el caolín y las arenas caoliníferas a temperaturas de 750ºC durante 3h, a moliendas hasta alcanzar su amorfización, y/o a activaciones con HCl 6M o con NaOH 5M durante 3h a 90ºC. En total se obtuvieron 18 muestras, en las que se estudiaron las características físico-químicas, mineralógicas y morfológicas de cada una de ellas con el fin de caracterizarlas después de haber sufrido los tratamientos y/o activaciones químicas. Los cambios producidos fueron estudiados mediante pH, capacidad de intercambio catiónico (CEC), capacidad de adsorción de agua (WCU y CWC), distribución de tamaño de partícula (PSD), área de superficie específica (SBET), difracción de rayos X (XRD), espectroscopía infrarroja por transformada de Fourier (FTIR), métodos térmicos (TG, DTG y DTA), y microscopía electrónica de transmisión y barrido (SEM y TEM). Además se analizó los cambios producidos por los tratamientos en función de las pérdidas de Al y Si que acontece en las 18 muestras. Los resultados para los materiales derivados de la arenas caoliníferas fueron similares a los obtenidos para los caolines lavados, la diferencia radica en la cantidad de contenido de caolinita en los diferente grupos de muestras. Apoyándonos en las técnicas de caracterización se puede observar que los tratamientos térmico y molienda produce materiales amorfos, este cambio en la estructura inicial sumado a las activaciones ácida y alcalina dan lugar a pérdidas de Si y Al, ocasionando que sus propiedades físico-químicas, mineralógicas y morfológicas se vean alteradas. Un fuerte aumento es observado en las áreas superficiales y en la CEC en determinadas muestras, además entre los cambios producidos se encuentra la producción de diferentes zeolitas en porcentajes distintos con el tratamiento alcalino. Para la obtención de las organoarcillas, las 18 muestras se sometieron a la surfactación con hexadeciltrimetil amonio (HDTMA) 20 mM durante 24h a 60ºC, esta concentración de tensioactivo fue más alta que la CEC de cada muestra. Los camext bios anteriormente producidos por los tratamientos y activaciones, afectan de forma diferente en la adsorción de HDTMA, variando por tanto la adsorción del surfactante en la superficie de las muestras. Se determinó el tensioactivo en superficie por FTIR, además se realizó un análisis de componentes principales (PCA) para examinar la dependencia entre las relaciones Si/Al de las muestras en la capacidad de adsorción de tensioactivo, y para el estudio de la adsorción de HDTMA en las muestras se realizaron además del análisis termogravimétrico, aproximaciones con los modelos de Freundllich y Langmuir. Se persigue conocer las diferentes formas y maneras que tiene el tensioactivo de fijarse en la superficie de las muestras. En las organoarcillas resultantes se cuantificó el fenol adsorbido cuando éstas fueron puestas en contacto con diferentes concentraciones de fenol: 50, 500, 1000, 2000, y 2500 mg/l durante 24h. El contaminante sorbido se calculó por medio de cromatografía de gases, y se realizaron aproximaciones con los modelos de Freundllich y Langmuir. El comportamiento de adsorción de fenol en arcillas orgánicas es regido por las características de las muestras. De forma general se puede decir que las muestras de caolines lavados tienen más capacidad de adsorción de fenol que las muestras de arenas de caolín y que la activación alcalina ha proporcionado una mejora en la adsorción de fenol en los dos grupos. En consecuencia se han obtenido materiales adsorbentes heterogéneos y por tanto, con propiedades diferentes. Se ha evaluado el comportamiento global de las arenas de caolín por un lado y del caolín lavado por otro. Las arenas de caolín presentan altos niveles de cuarzo y su uso para ciertos tipos de industrias no son recomendados en ocasiones por el alto costo que el proceso de limpieza y purificación implicaría. Por ello es importante reseñar en este proyecto las aplicaciones que ofrecen algunas muestras de este grupo. Los ensayos acontecidos en esta tesis han dado lugar a las siguientes publicaciones: • Pérdida de Al y Si en caolines modificados térmica- o mecánicamente y activados por tratamientos químicos. A. G. San Cristóbal, C Vizcayno, R. Castelló. Macla 9, 113-114. (2008). • Acid activation of mechanically and thermally modfied kaolins. A. G. San Cristóbal, R. Castelló, M. A. Martín Luengo, C Vizcayno. Mater. Res. Bull. 44 (2009) 2103-2111. • Zeolites prepared from calcined and mechanically modified kaolins. A comparative study. A. G San Cristóbal, R. Castelló, M. A. Martín Luengo, C Vizcayno. Applied Clay Science 49 (2010) 239-246. • Study comparative of the sorption of HDTMA on natural and modified kaolin. A. G San Cristóbal, R. Castelló, J. M. Castillejo, C Vizcayno. Aceptada en Clays and Clay minerals. • Capacity of modified kaolin sand and washed kaolin to adsorb phenol. A. G San Cristóbal, R. Castelló, C Vizcayno. Envío a revista sujeto a la publicación del artículo anterior. ABSTRACT Today’s chemical, pharmaceutical and clinical industries generate pollutants that affect the soils and surface and ground waters of our country. Among these, phenol is a common organic pollutant that is extremely harmful to living organisms, even at low concentrations. Several protocols exist to minimize the effects of pollutants, but most are costly procedures or even generate other pollutants. The adsorption of hazardous materials onto clays is perhaps the most used, efficient and cost-saving method available. However, organic compounds such as phenol are difficult to adsorb and this has led to the development of materials known as organoclays, which are much better at remediating organic compounds. Organoclays are clays that have been modified using a surfactant. In turn, surfactants are organic molecules that confer a cationic rather than anionic charge to the clay surface, improving it’s capacity to adsorb phenol. For this doctorate project, kaolin was selected as an adsorbent material for the removal of phenol given its easy sourcing and relatively low cost. The materials investigated were kaolin sand, a directly extracted material, and washed kaolin, which is the byproduct of the kaolin sand washing process. The main difference between the materials is their quartz content, which is much higher in the kaolin sands. To generate a product from kaolin or kaolin sand capable of retaining organic pollutants such as phenol, both materials were subjected to several heat, chemical and/or mechanical treatments to give rise to compounds with a greater reactive surface area. To this end the two starting materials underwent heating at 750ºC for 3 h, grinding to the point of amorphization and/or activation with HCl 6M or NaOH 5M for 3 h at 90ºC. These treatments gave rise to 18 processed samples, which were characterized in terms of their morphological, mineralogical, and physical-chemical properties. The behaviour of these new materials was examined in terms of their pH, cation exchange capacity (CEC), water adsorption capacity (WCU and WCC), particle size distribution (PSD), specific surface area (SBET), and their X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FTIR), thermal (DTG, DTA) and scanning and transmission electron microscopy (SEM and TEM) properties. The changes conferred by the different treatments were also examined in terms of Al and Si losses. Results for the materials derived from kaolin sands and washed kaolin were similar, with differences attributable to the kaolinite contents of the samples. The treatments heat and grinding produced amorphous materials, which when subjected to acid or alkali activation gave rise to Si and Al losses. This in turn led to a change in physico- chemical, mineralogical and morphological properties. Some samples showed a highly increased surface area and CEC. Further, among the changes produced, alkali treatment led to the generation of zeolites in different proportions depending on the sample. To produce the organoclays, the 18 samples were surfacted with hexadecyltrimethylammonium (HDTMA) 20 mM for 24 h at 60ºC. This surfactant concentration is higher than the CEC of each sample. The amount of HDTMA adsorbed onto the surface of each sample determined by FTIR varied according to treatment. A principle components analysis (PCA) was performed to examine correlations between sample Si/Al ratios and surfactant adsorption capacity. In addition, to explore HDTMA adsorption by the samples, DTG and DTA data were fitted to Freundllich and Langmuir models. The mechanisms of surfactant attachment to the sample surface were also addressed. The amount of phenol adsorbed by the resultant organoclays was determined when exposed to different phenol concentrations: 50, 500, 1000, 2000, and 2500 mg/l for 24 h. The quantity of adsorbed pollutant was estimated by gas chromatography and the data fitted to the models of Freundllich and Langmuir. Results indicate that the phenol adsorption capacity of the surfacted samples is dependent on the sample’s characteristics. In general, the washed kaolin samples showed a greater phenol adsorption capacity than the kaolon sands and alkali activation improved this capacity in the two types of sample. In conclusion, the treatments used gave rise to adsorbent materials with varying properties. Kaolin sands showed high quartz levels and their use in some industries is not recommended due to the costs involved in their washing and purification. The applications suggested by the data obtained for some of the kaolin sand samples indicate the added value of this industrial by-product. The results of this research project have led to the following publications: • Pérdida de Al y Si en caolines modificados térmica- o mecánicamente y activados por tratamientos químicos. A. G. San Cristóbal, C Vizcayno, R. Castelló. Macla 9, 113-114. (2008). • Acid activation of mechanically and thermally modfied kaolins. A. G. San Cristóbal, R. Castelló, M. A. Martín Luengo, C Vizcayno. Mater. Res. Bull. 44 (2009) 2103-2111. • Zeolites prepared from calcined and mechanically modified kaolins. A comparative study. A. G. San Cristóbal, R. Castelló, M. A. Martín Luengo, C Vizcayno. Applied Clay Science 49 (2010) 239-246. • Study comparative of the sorption of HDTMA on natural and modified kaolin. A. G. San Cristóbal, R. Castelló, J. M. Castillejo, C Vizcayno Accepted in Clays and Clay minerals. • Capacity of modified kaolin sand and washed kaolin to adsorb phenol. A. G San Cristóbal, R. Castelló, C Vizcayno. Shipment postponed, subject to the publication of the previous article.

Aprovechamiento térmico de residuos estériles de carbón para generación eléctrica mediante tecnologías de combustión y gasificación eficientes y con mínimo impacto ambiental

La presente tesis doctoral, “Aprovechamiento térmico de residuos estériles de carbón para generación eléctrica mediante tecnologías de combustión y gasificación eficientes y con mínimo impacto ambiental”, desarrolla la valorización energética de los residuos del carbón, estériles de carbón, producidos durante las etapas de extracción y lavado del carbón. El sistema energético se encuentra en una encrucijada, estamos asistiendo a un cambio en el paradigma energético y, en concreto, en el sector de la generación eléctrica. Se precipita un cambio en la generación y el consumo eléctricos. Una mayor concienciación por la salud está forzando la contención y eliminación de agentes contaminantes que se generan por la utilización de combustibles fósiles de la forma en la que se viene haciendo. Aumenta la preocupación por el cambio climático y por contener en 2°C el aumento de la temperatura de la Tierra para final de este siglo, circunstancia que está impulsando el desarrollo e implantación definitiva de tecnología de control y reducción de emisiones CO2. Generar electricidad de una manera sostenible se está convirtiendo en una obligación. Esto se materializa en generar electricidad respetando el medioambiente, de una forma eficiente en la utilización de los recursos naturales y a un coste competitivo, pensando en el desarrollo de la sociedad y en el beneficio de las personas. En la actualidad, el carbón es la principal fuente de energía utilizada para generar electricidad, y su empleo presenta la forma de energía más barata para mejorar el nivel de vida de cualquier grupo y sociedad. Además, se espera que el carbón siga presente en el mix de generación eléctrica, manteniendo una significativa presencia y extrayéndose en elevadas cantidades. Pero la producción de carbón lleva asociada la generación de un residuo, estéril, que se produce durante la extracción y el lavado del mineral de carbón. Durante décadas se ha estudiado la posibilidad de utilizar el estéril y actualmente se utiliza, en un limitado porcentaje, en la construcción de carreteras, terraplenes y rellenos, y en la producción de algunos materiales de construcción. Esta tesis doctoral aborda la valorización energética del estéril, y analiza el potencial aprovechamiento del residuo para generar electricidad, en una instalación que integre tecnología disponible para minimizar el impacto medioambiental. Además, persigue aprovechar el significativo contenido en azufre que presenta el estéril para producir ácido sulfúrico (H2SO4) como subproducto de la instalación, un compuesto químico muy demandado por la industria de los fertilizantes y con multitud de aplicaciones en otros mercados. Se ha realizado el análisis de caracterización del estéril, los parámetros significativos y los valores de referencia para su empleo como combustible, encontrándose que su empleo como combustible para generar electricidad es posible. Aunque en España se lleva extrayendo carbón desde principios del siglo XVIII, se ha evaluado para un período más reciente la disponibilidad del recurso en España y la normativa existente que condiciona su aplicación en el territorio nacional. Para el período evaluado, se ha calculado que podrían estar disponibles más de 68 millones de toneladas de estéril susceptibles de ser valorizados energéticamente. Una vez realizado el análisis de la tecnología disponible y que podría considerarse para emplear el estéril como combustible, se proponen cuatro configuraciones posibles de planta, tres de ellas basadas en un proceso de combustión y una de ellas en un proceso de gasificación. Tras evaluar las cuatro configuraciones por su interés tecnológico, innovador y económico, se desarrolla el análisis conceptual de una de ellas, basada en un proceso de combustión. La instalación propuesta tiene una capacidad de 65 MW y emplea como combustible una mezcla de carbón y estéril en relación 20/80 en peso. La instalación integra tecnología para eliminar en un 99,8% el SO2 presente en el gas de combustión y en más de un 99% las partículas generadas. La instalación incorpora una unidad de producción de H2SO4, capaz de producir 18,5 t/h de producto, y otra unidad de captura para retirar un 60% del CO2 presente en la corriente de gases de combustión, produciendo 48 tCO2/h. La potencia neta de la planta es 49,7 MW. Se ha calculado el coste de inversión de la instalación, y su cálculo resulta en un coste de inversión unitario de 3.685 €/kW. ABSTRACT The present doctoral thesis, “Thermal utilisation of waste coal for electricity generation by deployment of efficient combustion and gasification technologies with minimum environmental impact”, develops an innovative waste-to-energy concept of waste coals produced during coal mining and washing. The energy system is at a dilemma, we are witnessing a shift in the energy paradigm and specifically in the field of electricity generation. A change in the generation and electrical consumption is foreseen. An increased health consciousness is forcing the containment and elimination of pollutants that are generated by the use of fossil fuels in the way that is being done. Increasing concern about climate change and to contain the rise of global temperature by 2°C by the end of this century, is promoting the development and final implementation of technology to control and reduce the CO2 emission. Electricity generation in a sustainable manner is becoming an obligation. This concept materialised in generating electricity while protecting the environment and deployment of natural resources at a competitive cost, considering the development of society and people´s benefit. Currently, coal is the main source of energy employ to generate electricity, and its use represents the most cost competitive form of energy to increase the standard of living of any group or society. Moreover, coal will keep playing a key role in the global electricity generation mix, maintaining a significant presence and being extracting in large amounts. However, coal production implies the production of waste, termed waste coal or culm in Pennsylvania anthracite extraction, produced during coal mining and coal washing activities. During the last decades, the potential use of waste coal has been studied, and currently, in a limited amount, waste coal is used in roads construction, embankments and fillings, and to produce some construction materials. This doctoral thesis evaluates the waste to energy of waste coals and assesses its potential use to generate electricity, implementing available technology to minimise the environment impact. Additionally, it pursues the significant advantage that presents sulphur content in waste coal to produce sulphuric acid (H2SO4) as a byproduct of the waste-to-energy process, a chemical compound highly demanded by the fertiliser industry and many applications in other markets. It analyses the characteristics of waste coal, and assesses the significant parameters and reference values for its use as fuel, being its fuel use for electricity generation very possible. While mining coal is taking place in Spain since the 1700s, it has been evaluated for a more recent period the waste coal available in Spain and the existing legislation that affects its application and deploy to generate electricity in the country. For the evaluation period has been calculated that may be available more than 68 million tons of waste coal that can be waste-toenergy. The potential available technology to deploy waste coal as fuel has been evaluated and assessed. After considering this, the doctoral thesis proposes four innovative alternatives of facility configuration, three of them based on a combustion process and one in a gasification process. After evaluating the four configurations for its technological, innovative and economic interest, the conceptual analysis of one of alternatives, based on a combustion process, takes place. The proposed alternative facility developed has a capacity of 65 MW, using as fuel a mixture of coal and waste coal 80/20 by weight. The facility comprises technology to remove 99.8% SO2 present in the flue gas and more than 99% of the particles. The facility includes a unit capable of producing 18.5 t/h of H2SO4, and another capture facility, removing 60% of CO2 present in the flue gas stream, producing 48 tCO2/h. The net capacity of the power station is 49.7 MW. The facility unitary cost of investment is 3,685 €/kW.

Biomarcatori per il monitoraggio biologico di soggetti esposti ad agenti cancerogeni per il polmone

Riassunto I biomarcatori o “marcatori biologici” svolgono un ruolo fondamentale nel monitoraggio biologico. In questo lavoro ci siamo soffermati sullo studio di biomarcatori di effetto e di esposizione a xenobiotici ambientali. Nel primo caso abbiamo valutato i micro RNA (miRNA) da utilizzare per la diagnosi precoce del tumore al polmone in matrici di facile accesso, quale il CAE e il plasma, utilizzando il miRNA-21, oncogeno, e il miRNA-486, oncosoppressore. I risultati evidenziano una loro capacità di distinguere correttamente i soggetti con tumore polmonare dai soggetti sani, ipotizzando un loro utilizzo a scopo diagnostico. Nella seconda parte del lavoro di tesi sono stati studiati i biomarcatori di esposizione a benzene per valutare gli effetti dell’esposizione a concentrazioni ambientali su bambini residenti in città e a diverso livello di urbanizzazione. Lo studio ha evidenziato una correlazione dose-effetto fra le concentrazioni di benzene e dei suoi metaboliti urinari e un danno ossidativo a livello degli acidi nucleici. Tuttavia, le concentrazioni di benzene urinario non sono influenzate dal grado di industrializzazione, a differenza dell’S-PMA e degli indicatori di stress ossidativo (8-oxodGuo e 8-oxoGuo) che sembrano risentire sia della residenza che del momento del campionamento. Infine abbiamo ricercato possibili biomarcatori di esposizione a vinilcicloesene (VCH), sottoprodotto industriale nella polimerizzazione del 1,3-butadiene, poiché non sono ancora stati proposti BEI di riferimento nonostante i bassi valori di TLV-TWA (0.1 ppm) proposti dall’ACGIH. Nella prima fase del lavoro abbiamo studiato i meccanismi di tossicità del VCH tramite modelli in vitro, testando varie linee cellulari. I risultati evidenziano come la dose reale di VCH sia di molto inferiore a quella nominale per effetto dell’evaporazione. Inoltre, nelle linee cellulari più sensibili si sono evidenziati effetti citostatici, con alterazioni del ciclo cellulare, a differenza dell’esposizione agli epossidi del VCH, il VCD e l’1,2-VCHME, che determinano lisi cellulare con IC50 di 3 ordini di grandezza inferiori a quelli del VCH. La quantificazione dei metaboliti di I fase e di II fase del VCH nelle linee cellulari epatiche ha evidenziato concentrazioni di circa 1000 volte inferiori a quelle del VCH confermando come la sua tossicità sia principalmente dovuta alla produzione degli intermedi epossidici. La trasformazione nei metaboliti di II fase conferma inoltre l’effetto detossificante del metabolismo. La trasferibilità dei risultati ottenuti in vitro su sistemi in vivo fornirà le basi per poter identificare possibili metaboliti da proporre per il monitoraggio biologico di lavoratori esposti a VCH. PAROLE CHIAVE: biomarcatori di effetto e di esposizione, tumore al polmone, miRNA, benzene, vinilcicloesene.

Minimização de resíduos do processamento do café solúvel através do reaproveitamento da borra para extração de óleo utilizando solvente renovável

O principal resíduo da indústria de café solúvel é a borra de café, gerada após a extração de sólidos solúveis com água, sendo usualmente queimada em caldeiras para geração de energia para a própria indústria. Entretanto, este co-produto pode conter de 15 a 20 % de óleo, componente de grande interesse na indústria alimentícia. Em paralelo, na indústria de produção de óleos vegetais o solvente frequentemente utilizado é o hexano. Contudo, por este ser um derivado de combustíveis fósseis, alternativas para sua substituição por solventes mais amigáveis ao meio ambiente, que podem ser obtidos por via biotecnológica, estão sendo estudadas. Deste modo, o objetivo principal desta dissertação de mestrado foi a viabilização técnica do emprego de solventes alcoólicos no processo de extração de óleo de borra de café proveniente da indústria de processamento de café solúvel. Foram realizadas extrações sólido-líquido em um estágio para estudar a influência das variáveis de processo temperatura (60 a 90 °C), tipo de solvente (etanol, ET ou isopropanol, IPA) e a hidratação do solvente (absoluto ou azeotrópico) nas características das fases extrato e rafinado, em termos de rendimento de extração de óleo, de ácidos clorogênicos (ACG), de carboidratos totais, teor de proteínas e índice de solubilidade de nitrogênio (ISN) da fase rafinado. Pré-tratamento enzimático ao processo de extração também foi realizado para investigar a sua atuação sobre o rendimento de extração de óleo e ACG, além do ISN das fases rafinado obtidas na temperatura de 70 °C. De forma geral, pode-se inferir que a temperatura favorece a extração de compostos lipídicos, mas a hidratação do solvente prejudica a extração destes compostos pelo aumento da polaridade do solvente. Do mesmo modo, como o ET é mais polar que o IPA, o primeiro solvente proporcionou a obtenção de menores rendimentos de extração de óleo. A temperatura de processo também influenciou a extração de ACG, a qual foi beneficiada a temperaturas mais baixas pelo aumento da polaridade dos solventes utilizados. De tal forma, que a 60 °C, nos experimentos utilizando etanol azeotrópico obteve-se os menores rendimentos de extração de óleo, porém maior rendimento de extração de ACG. O pré-tratamento enzimático apresentou diferenças significativas nas características das fases extrato e rafinado. No entanto, somente os experimentos com etanol absoluto resultaram em rendimentos de extração de óleo economicamente viáveis. De fato, será relevante um estudo mais aprofundado das variáveis de pré-tratamento enzimático para obter resultados mais expressivos em relação à extração de compostos lipídicos. Diante dos dados experimentais obtidos, conclui-se que é tecnicamente viável o emprego de solventes alcoólicos no processo de extração de óleo de borra de café. Entretanto, nota-se que as condições de processo devem ser avaliadas minuciosamente com o objetivo de se obter altos rendimentos de extração de óleo com maior teor de ACG.

Groups, information theory, and Einstein's likelihood principle

We propose a unifying picture where the notion of generalized entropy is related to information theory by means of a group-theoretical approach. The group structure comes from the requirement that an entropy be well defined with respect to the composition of independent systems, in the context of a recently proposed generalization of the Shannon-Khinchin axioms. We associate to each member of a large class of entropies a generalized information measure, satisfying the additivity property on a set of independent systems as a consequence of the underlying group law. At the same time, we also show that Einstein's likelihood function naturally emerges as a byproduct of our informational interpretation of (generally nonadditive) entropies. These results confirm the adequacy of composable entropies both in physical and social science contexts.

Gaseificação de vinhaça em água supercrítica.

A gaseificação utiliza o conteúdo intrínseco de carbonos e hidrogênios das matérias primas sólidas ou líquidas na geração de uma mistura de hidrogênio (H2), monóxido de carbono (CO), dióxido de carbono (CO2) e metano (CH4). Tal mistura pode ser utilizada como matéria prima na síntese de novos produtos ou como combustível. A gaseificação pode ser utilizada no processamento de uma gama variada de produtos, independentemente de suas características ou estado físico. A utilização de biomassa como insumo da gaseificação vem sendo cada vez mais explorada e estudada, já que apresenta benefícios não somente na esfera ambiental, mas também em âmbitos econômicos e sociais. A vinhaça é um subproduto do processo de produção de álcool, que contém grandes concentrações de nutrientes e matéria orgânica em sua composição. A sua utilização hoje está limitada a fertirrigação e a aplicações isoladas em biodigestão e outros, que não são suficientes para o consumo da produção anual crescente do resíduo. Seu uso na gaseificação permitiria o aproveitamento do conteúdo orgânico da mesma e a produção de gases de alto valor agregado. Como a umidade do insumo interfere negativamente na eficiência da gaseificação clássica, a aplicação da mesma para matérias primas com alto teor de líquidos não é recomendada. Uma alternativa viável seria a utilização do meio gaseificante supercrítico, que resulta em rendimentos constantes, independentemente da umidade da corrente de entrada do reator. O presente trabalho consiste no projeto de um módulo de gaseificação de vinhaça em água supercrítica, a ser instalado como uma unidade anexa a usinas de açúcar e álcool. Ele compreende o projeto conceitual e análise de viabilidade deste módulo, incluindo estimativas de CAPEX (Capital Expenditure) e OPEX (Operation Expenditure) e uma análise de sensibilidade dos mesmos. O estudo apresenta ainda o estado da arte do conhecimento e da tecnologia de gaseificação com água supercrítica (SCWG), relacionando os gargalos a serem resolvidos, assim como os ganhos intrínsecos da definição conceitual do projeto.

The preparation of leucylalanine-2-C¹⁴ /

L-Leucyl-DL-alanine-2-C¹⁴ with a specific activity of 2.5 uc/mg was prepared in an over-all yield of 22% from alanine-2-c¹⁴. Thirty-three percent of the starting activity was recovered as DL-alanine-2-C¹⁴. A byproduct of the reaction in a yield of 22% was tentatively identified as an intra-or intermolecular anhydride of the peptide.

Estimating the Extent of Soil Contamination During a Redevelopment Excavation

From October 2014 to March 2015, I provided excavation oversight services at a property with substantial environmental concerns. The property in question is located near downtown Seattle and was formerly occupied by the Washington’s first coal gasification plant. The plant operated from 1888 to 1908 and produced coal gas for municipal use. A coal tar like substance with a characteristically high benzene concentration was a byproduct of the coal gasification process and heavily contaminated at or below the surface grade of the plant as shown in previous investigations on the property. Once the plant ceased operation in 1908 the property was left vacant until 1955 when the site was filled in and a service station was built on the property. The main goal of the excavation was not to achieve cleanup on the property, but to properly remove what contaminated soil was encountered during the redevelopment excavation. Areas of concern were identified prior to the commencement of the excavation and an estimation of the extent of contamination on the property was developed. “Hot spots” of contaminated soil associated with the fill placed after 1955 were identified as areas of concern. However, the primary contaminant plume below the property was likely sourced from the coal gasification plant, which operated at an approximate elevation of 20 feet. We planned to constrain the extents of the soil contamination below the property as the redevelopment excavation progressed. As the redevelopment excavation was advanced down to an elevation of approximately 20 feet, soil samples were collected to bound the extents of contamination in the upper portion of the site. The hot spots, known pockets of carcinogenic polycyclic aromatic hydrocarbons (cPAH) located above 20 feet elevation, were excavated as part of the redevelopment excavation. Once a hot spot was excavated, soil samples were collected from the north, south, east, west and bottom sidewalls of the hot spot excavation to check for remaining cPAH. Additionally, four underground storage tanks (USTs) associated with the service station were discovered and subsequently removed. Soil samples were also collected from the resulting UST excavation sidewalls to check for remaining petroleum hydrocarbons. Once the excavation reached its final excavation depth of 20 to 16 feet in elevation, bottom of excavation samples were collected on a 35 foot by 35 foot grid to test for concentrations of contaminants remaining onsite. Once the redevelopment excavation was complete, soils observed from borings drilled for either structural elements, geotechnical wells, or environmental wells were checked for any evidence of contamination using field screening techniques. Evidence of contamination was used to identify areas below the final excavation grade which had been impacted by the operation of the coal gasification plant. Samples collected from the excavation extents of hot spots and USTs show that it was unlikely that any contamination traveled from the post-1955 grade down to the pre-1955 grade. Additionally, the lack of benzene in the bottom of excavation samples suggests that a release from the coal gasification plant occurred below the redevelopment excavation final elevations of 20 to 16 feet. Qualitative data collected from borings for shoring elements and wells indicated that the spatial extent of the subsurface contaminant plume was different than initially estimated. Observations of spoils show that soil contamination extends further to the southwest and not as far to the east and north than originally estimated. Redefining the extent of the soil contamination beneath the property will allow further subsurface investigations to focus on collecting quantitative data in areas that still represent data gaps on the property, and passing over areas that have shown little signs of contamination. This information will help with the formation of a remediation plan should the need to clean up the site arise in the future.

An investigation of contaminant distribution in subsurface marine wood waste at Mill-A South Terminal, Port of Everett, Washington

This project investigates the correlation between contaminants and the wood waste present in marine sediments off the shore of the Port of Everett in the former Weyerhaeuser Mill-A pulp mill site. The investigation includes the results of two field studies, which tested contaminant levels in 22 boreholes as well as several surface samples. The contaminants include heavy metals and wood waste byproducts. These results, along with 14 other bore logs, provide the framework for a three-dimensional site model, interpolating the full extent of the depositional units and organic and inorganic chemicals found at Mill-A. The sediments of interest are divided into five depositional units defined by the percent wood content and type of wood: native material (<5% wood), intermediate (<30% wood), sawdust (<30% wood), woodchips (<30% wood), and poorly sorted sands with silt (SM-SP) (0% wood). The contaminants include arsenic, 2,4-dimethylphenol, and total organic carbon. Three-dimensional modeling software, RockWorks, interpolated the discrete borehole data of sediment and contaminants assuming horizontal continuity between sampling locations. The sediment distribution was calculated within concentration ranges for each contaminant of concern. The lowest detection limits, the screening levels, and the cleanup levels defined these ranges. Total organic carbon served as a proxy to estimate the quantity of wood waste in the sediment. As a known byproduct of wood decomposition, 2,4-dimethylphenol was expected to be more prevalent in the depositional units with more wood waste. Finally, arsenic was a proxy for other contaminants to determine if contaminants at Mill-A are dominant in sediments with high percentages of wood waste. The volumetric distribution established that high levels of total organic carbon are present in the sediment with higher percentages of wood waste. This correlation was stronger in the decomposing sawdust-rich sediment than the woodchip-rich sediment. The 2,4-dimethylphenol concentrations above cleanup standards were dominant in the sawdust-rich, intermediate and native sediments. Concentrations of 2,4-dimethylphenol below cleanup levels characterized the native sediment. The distribution of arsenic showed no statistically significant correlation to wood content in sediment. These results do not support the hypothesis of contaminant-rich wood waste, as many of the high concentrations of contaminants were not in the wood-rich sediments. This suggests that the contaminants are more distributed among all depositional units at Mill-A rather than focused within sediments with a high percent of wood waste. Understanding the distribution of potentially toxic compounds with wood waste is important for restoring the Puget Sound waterways to a more habitable environment. Future studies should include new data to validate these results and to limit the uncertainty of the extent of contaminants. Future studies may also find motive in looking for a correlation between contaminants and grain size based on previous studies linking these characteristics. These investigations will benefit the current cleanup effort as well as future cleanup efforts at similarly contaminated waterways.