Plaster reinforcement with fibers by mineral wool obtained from the recycle of construction and demolition waste

The use of mineral wool is becoming more widespread due to increased acoustic and thermal demands of Spanish Technical Building Code. This increase affects both in rehabilitation and new construction projects. Therefore, waste generation of this type of insulating material is having more importance. The main objective of this research is to study the possibility of recycling fiber obtained from mineral wool of the C&DW as an alternative material to chopped glass fibers that are currently used as reinforcing elements in the prefabricated plaster. To achieve this objective, series are made of plaster E-35 additived with rock wool residue and glass wool residue at different rates of addition. These series are repeated by changing the additive by E fiberglass (length of 25mm) to make a comparative analysis with respect to the series additived with mineral wool waste. All the series are subjected to the test to determine Shore C surface hardness and mechanical testing to determine the compressive and flexural strength. From the results it can be concluded that: with rock wool residue, increases Shore C hardness up to 15% with respect to the glass fiber and 9% with respect to the glass wool, with a percentage of addition 2%. With rock wool residue, weight is decreased by 5% with respect to the glass fiber and 4% with respect to the glass wool waste, with an addition percentage of 4%. For an addition rate of 4%, results in the flexural strength test with fiberglass are 85% higher than those obtained with glass wool residue. However, for a percentage of 1% addition, the results obtained with glass wool residue are 35% higher than those obtained with fiberglass. For an addition rate of 3% results in the compressive strength test with fiberglass are 54% lower than those obtained with rock wool waste and 70% lower than those obtained with glass wool waste. Comparing the two mineral wools, it can be concluded that up to 3% of the addition, the glass wool series results obtained are 10% higher than those additived with rock wool. However, higher percentages of addition show that the results obtained with rock wool are 35% higher than those obtained with glass wool. The general conclusion is that the series additived with mineral wool from C&DW show better results in tests than the ones used nowadays as plaster reinforcement.

Carbon dioxide emissions from semi-arid soils amended with biochar alone or combined with mineral and organic fertilizers

Semi-arid soils cover a significant area of Earth s land surface and typically contain large amounts of inorganic C. Determining the effects of biochar additions on CO2 emissions fromsemi-arid soils is therefore essential for evaluating the potential of biochar as a climate change mitigation strategy. Here, we measured the CO2 that evolved from semi-arid calcareous soils amended with biochar at rates of 0 and 20 t ha?1 in a full factorial combination with three different fertilizers (mineral fertilizer, municipal solid waste compost, and sewage sludge) applied at four rates (equivalent to 0, 75, 150, and 225 kg potentially available N ha?1) during 182 days of aerobic incubation. A double exponential model, which describes cumulative CO2 emissions from two active soil C compartments with different turnover rates (one relatively stable and the other more labile), was found to fit verywell all the experimental datasets. In general, the organic fertilizers increased the size and decomposition rate of the stable and labile soil C pools. In contrast, biochar addition had no effects on any of the double exponential model parameters and did not interact with the effects ascribed to the type and rate of fertilizer. After 182 days of incubation, soil organic and microbial biomass C contents tended to increase with increasing the application rates of organic fertilizer, especially of compost, whereas increasing the rate of mineral fertilizer tended to suppress microbial biomass. Biochar was found to increase both organic and inorganic C contents in soil and not to interactwith the effects of type and rate of fertilizer on C fractions. As a whole, our results suggest that the use of biochar as enhancer of semi-arid soils, either alone or combined with mineral and organic fertilizers, is unlikely to increase abiotic and biotic soil CO2 emissions.

Los residuos de envases y embalajes en edificación residencial. Patrones de generación y estrategias de mejora de su gestión

Uno de los retos a los que se enfrenta la humanidad es la demanda de una sociedad con casi cero residuos: la búsqueda de una economía más eficiente en el uso de los recursos teniendo en cuenta el cambio climático y un abastecimiento sostenible de materias primas que permitan satisfacer las necesidades de una población mundial cada vez mayor, dentro de los límites sostenibles de los recursos naturales del planeta. Abordar este desafío implica la recuperación y reciclaje de materiales para reducir consumos de materias primas y, para ello, debe promoverse la innovación en la prevención y gestión de residuos, como estrategia hacia un desarrollo urbano sostenible. Los envases y embalajes forman parte de la cultura actual, relacionándose con el grado de desarrollo de países y regiones; el sector de la construcción no es ajeno a la problemática y genera un importante volumen de embalajes en las obras que no se gestionan de forma adecuada. El modelo de gestión de Residuos de Construcción Demolición (RCD) actual es poco eficaz, ya que los vertederos siguen recibiendo grandes cantidades de residuos valorizables. La normativa ha conseguido minimizar las prácticas ilegales, pero se comprueba que la gestión actual de los RCD en obra deja en manos de las plantas de tratamiento la misión de separar los residuos según su naturaleza y los datos aportados por las distintas plantas no permiten afirmar el grado de alcance de dicho objetivo, ni el destino de los mismos. Los envases y embalajes son un tipo de residuos que por su naturaleza suponen una fuente de recursos valorizables y por ello están presentes en directivas y leyes, dirigidas fundamentalmente al sector de la alimentación. En el ámbito de la construcción, hasta la fecha, no se habían tratado de forma específica, motivo que justifica este trabajo. Esta Tesis Doctoral tiene como objetivo principal mejorar la gestión de residuos de embalajes procedentes de materiales de construcción. Para ello se estudia un importante conjunto de obras de edificación residencial colectiva de 1173 viviendas, análisis que llevará a conocer los patrones de producción de los Residuos de Envases y Embalajes en Construcción (REEC) e identificar los productos o materiales responsables de su generación. La monitorización realizada, permitirá diseñar estrategias específicas que minimicen la generación de estos residuos y optimicen su valorización. Se ha podido comprobar que el tratamiento particularizado de los REEC puede mejorar los resultados de la gestión del conjunto de RCD, debido a que, al no mezclarse, se elimina un importante agente contaminador de los residuos inertes. Las obras analizadas alcanzan un nivel de segregación in situ muy bajo, y los capítulos de cerramientos e instalaciones suman más del 50% del global de REEC. Particularizando en cada tipo de material, el cartón predomina en los trabajos de electricidad, el plástico en las particiones y la madera en fachadas. Se evalúa la opción del eco-­‐rediseño para uno de los embalajes predominantes, y se identifican estrategias para minimizar su impacto. Se comprueba que el ahorro en la gestión de RCD en caso de impulsar la segregación in situ no es muy significativo en las obras estudiadas, si bien se demuestra que la viabilidad económica es el factor más importante para motivar a las empresas constructoras. Las Administraciones Públicas deberían incentivar la gestión responsable, estableciendo medidas de control en las plantas de tratamiento e implementando en sus obras medidas de gestión de RCD ejemplares para el mercado. Una adecuada planificación de la obra, y formación específica para el personal son medidas que facilitan la segregación in situ y mejoran los resultados. Los promotores, mediante su relación contractual con el resto de agentes, tienen la capacidad de establecer objetivos de reducción, planificación y gestión sostenible de los REEC. Por último, se propone un sistema de gestión de REEC, integrable dentro del Sistema de Gestión de la empresa constructora, que permite evitar que residuos valorizables tales como los envases y embalajes se envíen a vertedero, guiando al sector hacia un futuro más respetuoso, alineado con el desarrollo sostenible. ABSTRACT One of the challenges humanity faces is the demand of an almost zero waste society: the search for a more efficient economy in the use of resources, taking into account climate change and a sustainable supply of raw materials, that meet the needs of an increasing world population within the sustainable limits of the planet's natural resources. Addressing this challenge involves the recovery and recycling of materials to reduce consumption of raw materials, so innovation must therefore be promoted in the prevention and management of waste, as a strategy towards a sustainable urban development. Packaging is part of our current culture and is related to the degree of development of countries and regions; the construction sector is no stranger to this problem and generates a significant amount of packaging waste in the site works, which nowadays is not managed properly. The current Construction Demolition Waste (CDW) management model is ineffective, since landfills continue to receive large amounts of recoverable waste. The legislation has managed to minimize illegal practices, but it has been observed that the current management of CDW in the analysed works leaves the mission of separating waste according to their nature to the plants, and data provided by the latter does not allow for checking the scope of this objective, nor the destiny of the waste. Packaging is a type of waste which, by its nature, represents a source of recoverable resources and is therefore present in directives and laws, focused primarily on the food industry. It has not been specifically treated to date in the construction field, hence the reason that justifies this work. This Thesis aims to improve the management of packaging waste from construction materials. An important set of residential building works with 1173 dwellings is analysed, which leads to knowledge on the production patterns of packaging waste (PW) in the construction industry, and the identification of the products responsible for its generation. The monitorization also allows for the design of specific strategies which minimise the generation of waste and optimize recovery. It has been found that the individualized treatment of PW can improve the results of the management of the whole CDW since, when not mixed, a major pollutant of inert waste is removed. The analysed works reached a very low segregation level and the façades and building services phases account for more than 50% of the overall PW. Focusing on each type of material, cardboard predominates electricity works, plastic on partitions and wood on façades. Eco-­‐redesign is evaluated for one of the predominant packages, and strategies are identified to minimise their impact are . There is evidence that the savings in the CDW management in case of promoting segregation on site are not very significant at the studied works, although economic feasibility is the most important factor to motivate the construction companies. Public Administrations should encourage responsible management, establishing control measures in treatment plants and implementing CDW management exemplary measures on their work sites for the market. A proper planning of the works and specific training for the personnel are measures that facilitate in situ segregation and improve outcomes. The developers, through their contractual relationship with the other agents, have the ability to set reduction targets, planning and sustainable management of PW. Finally, a management system for PW is proposed, integrated within the Management System of the construction company, which aims to avoid that recoverable waste such as packaging is sent to landfill, leading the industry towards a more environmentally friendly future, aligned with sustainable development.

Asphalt rubber mixtures with warm mix asphalt additives

En los últimos años, debido a la creciente preocupación por el calentamiento global y el cambio climático, uno de los retos más importantes a los que se enfrenta nuestra sociedad es el uso eficiente y económico de energía así como la necesidad correspondiente de reducir los gases de efecto invernadero (GEI). Las tecnologías de mezclas semicalientes se han convertido en un nuevo e importante tema de investigación en el campo de los materiales para pavimentos ya que ofrece una solución potencial para la reducción del consumo energético y las emisiones de GEI durante la producción y puesta en obra de las mezclas bituminosas. Por otro lado, los pavimentos que contienen polvo de caucho procedente de neumático fuera de uso, al hacer uso productos de desecho, ahorran energía y recursos naturales. Estos pavimentos ofrecen una resistencia mejorada a la formación de roderas, a la fatiga y a la fisuración térmica, reducen los costes de mantenimiento y el ruido del tráfico así como prolongan la vida útil del pavimento. Sin embargo, estas mezclas presentan un importante inconveniente: la temperatura de fabricación se debe aumentar en comparación con las mezclas asfálticas convencionales, ya que la incorporación de caucho aumenta la viscosidad del ligante y, por lo tanto, se producen mayores cantidades de emisiones de GEI. En la presente Tesis, la tecnología de mezclas semicalientes con aditivos orgánicos (Sasobit, Asphaltan A, Asphaltan B, Licomont) se incorporó a la de betunes de alta viscosidad modificados con caucho (15% y 20% de caucho) con la finalidad de dar una solución a los inconvenientes de mezclas con caucho gracias a la utilización de aditivos reductores de la viscosidad. Para este fin, se estudió si sería posible obtener una producción más sostenible de mezclas con betunes de alto contenido en caucho sin afectar significativamente su nivel de rendimiento mecánico. La metodología aplicada para evaluar y comparar las características de las mezclas consistió en la realización de una serie de ensayos de laboratorio para betunes y mezclas con caucho y con aditivos de mezclas semicalientes y de un análisis del ciclo de vida híbrido de la producción de mezclas semicalientes teniendo en cuenta la papel del aditivo en la cadena de suministro con el fin de cuantificar con precisión los beneficios de esta tecnología. Los resultados del estudio indicaron que la incorporación de los aditivos permite reducir la viscosidad de los ligantes y, en consecuencia, las temperaturas de producción y de compactación de las mezclas. Por otro lado, aunque la adición de caucho mejoró significativamente el comportamiento mecánico de los ligantes a baja temperatura reduciendo la susceptibilidad al fenómeno de fisuración térmica, la adición de las ceras aumentó ligeramente la rigidez. Los resultados del estudio reológico mostraron que la adición de porcentajes crecientes de caucho mejoraban la resistencia del pavimento con respecto a la resistencia a la deformación permanente a altas temperaturas y a la fisuración térmica a bajas temperaturas. Además, se observó que los aditivos mejoran la resistencia a roderas y la elasticidad del pavimento al aumentar el módulo complejo a altas temperaturas y al disminuir del ángulo de fase. Por otra parte, el estudio reológico confirmó que los aditivos estudiados aumentan ligeramente la rigidez a bajas temperaturas. Los ensayos de fluencia llevados a cabo con el reómetro demostraron una vez más la mejora en la elasticidad y en la resistencia a la deformación permanente dada por la adición de las ceras. El estudio de mezclas con caucho y aditivos de mezclas semicalientes llevado a cabo demostró que las temperaturas de producción/compactación se pueden disminuir, que las mezclas no experimentarían escurrimiento, que los aditivos no cambian significativamente la resistencia conservada y que cumplen la sensibilidad al agua exigida. Además, los aditivos aumentaron el módulo de rigidez en algunos casos y mejoraron significativamente la resistencia a la deformación permanente. Asimismo, a excepción de uno de los aditivos, las mezclas con ceras tenían la misma o mayor resistencia a la fatiga en comparación con la mezcla control. Los resultados del análisis de ciclo de vida híbrido mostraron que la tecnología de mezclas semicalientes es capaz de ahorrar significativamente energía y reducir las emisiones de GEI, hasta un 18% y 20% respectivamente, en comparación con las mezclas de control. Sin embargo, en algunos de los casos estudiados, debido a la presencia de la cera, la temperatura de fabricación debe reducirse en un promedio de 8 ºC antes de que los beneficios de la reducción de emisiones y el consumo de combustible puedan ser obtenidos. Los principales sectores contribuyentes a los impactos ambientales generados en la fabricación de mezclas semicalientes fueron el sector de los combustibles, el de la minería y el de la construcción. Due to growing concerns over global warming and climate change in recent years, one of the most important challenges facing our society is the efficient and economic use of energy, and with it, the corresponding need to reduce greenhouse gas (GHG) emissions. The Warm Mix Asphalt (WMA) technology has become an important new research topic in the field of pavement materials as it offers a potential solution for the reduction of energy consumption and GHG emissions during the production and placement of asphalt mixtures. On the other hand, pavements containing crumb-rubber modified (CRM) binders save energy and natural resources by making use of waste products. These pavements offer an improved resistance to rutting, fatigue and thermal cracking; reduce traffic noise and maintenance costs and prolong pavement life. These mixtures, however, present one major drawback: the manufacturing temperature is higher compared to conventional asphalt mixtures as the rubber lends greater viscosity to the binder and, therefore, larger amounts of GHG emissions are produced. In this dissertation the WMA technology with organic additives (Sasobit, Asphaltan A, Asphaltan B and Licomont) was applied to CRM binders (15% and 20% of rubber) in order to offer a solution to the drawbacks of asphalt rubber (AR) mixtures thanks to the use of fluidifying additives. For this purpose, this study sought to determine if a more sustainable production of AR mixtures could be obtained without significantly affecting their level of mechanical performance. The methodology applied in order to evaluate and compare the performance of the mixtures consisted of carrying out several laboratory tests for the CRM binders and AR mixtures with WMA additives (AR-WMA mixtures) and a hybrid input-output-based life cycle assessment (hLCA) of the production of WMA. The results of the study indicated that the incorporation of the organic additives were able to reduce the viscosity of the binders and, consequently, the production and compaction temperatures. On the other hand, although the addition of rubber significantly improved the mechanical behaviour of the binders at low temperatures reducing the susceptibility to thermal cracking phenomena, the addition of the waxes slightly increased the stiffness. Master curves showed that the addition of increasing percentages of rubber improved the resistance of the pavement regarding both resistance to permanent deformation at high temperatures and thermal cracking at low temperatures. In addition, the waxes improved the rutting resistance and the elasticity as they increased the complex modulus at high temperatures and decreased the phase angle. Moreover, master curves also attest that the WMA additives studied increase the stiffness at low temperatures. The creep tests carried out proved once again the improvement in the elasticity and in the resistance to permanent deformation given by the addition of the waxes. The AR-WMA mixtures studied have shown that the production/compaction temperatures can be decreased, that the mixtures would not experience binder drainage, that the additives did not significantly change the retained resistance and fulfilled the water sensitivity required. Furthermore, the additives increased the stiffness modulus in some cases and significantly improved the permanent deformation resistance. Except for one of the additives, the waxes had the same or higher fatigue resistance compared to the control mixture. The results of the hLCA demonstrated that the WMA technology is able to significantly save energy and reduce GHG emissions, up to 18% and 20%, respectively, compared to the control mixtures. However, in some of the case studies, due to the presence of wax, the manufacturing temperature at the asphalt plant must be reduced by an average of 8ºC before the benefits of reduced emissions and fuel usage can be obtained. The results regarding the overall impacts generated using a detailed production layer decomposition indicated that fuel, mining and construction sectors are the main contributors to the environmental impacts of manufacturing WMA mixtures.

Managing Soil Organic Carbon: A Farm Perspective

Farming practices that lead to declining returns and inputs of carbon to soils pose a threat to key soil functions. The EU FP 7 interdisciplinary project Smart SOIL is using scientific testing and modeling to identify management practices that can optimize soil carbon storage and crop productivity. A consultation with advisors and policymakers in six European case study regions seeks to identify barriers to, and incentives for, uptake of such practices. Results from preliminary interviews are reported. Overall advisor and farmer awareness of management practices specifically directed towards soil carbon. is low. Most production- related decisions are taken in the short term, but managing soil carbon needs a long- term approach. Key barriers to uptake of practices include: perceived scientifi c uncertainty about the effi cacy of practices; lack of real life ?best practice? examples to show farmers; diffi culty in demonstrating the positive effects of soil carbon management practices and economic benefi ts over a long time scale; and advisors being unable to provide suitable advice due to inadequate information or training. Most farmers are unconvinced of the economic benefi ts of practices for managing soil carbon. Incentives are therefore needed, either as subsidies or as evidence of the cost effectiveness of practices. All new measures and advice should be integrated into existing programmes to avoid a fragmented policy approach.

Risk of Leaching in Soils Amended by Compost and digestate from Municipal Solid Waste

New European directives have proposed the direct application of compost and digestate produced from municipal solid wastes as organic matter sources in agricultural soils. Therefore information about phosphorus leaching from these residues when they are applied to the soil is increasingly mportant. Leaching experiments were conducted to determine the P mobility in compost and digestate mixtures, supplying equivalent amounts to 100 kg P ha?1 to three different types of soils. The tests were performed in accordance with CEN/TS 14405:2004 analyzing the maximum dissolved reactive P and the kinetic rate in the leachate. P biowaste fractionation indicated that digestate has a higher level of available P than compost has. In contrast, P losses in leaching experiments with soil-compost mixtureswere higher than in soil-digestate mixtures. For bothwastes, therewas no correlation between disolved reactive P lost and the water soluble P.The interaction between soil and waste, the long experimentation time, and the volume of leachate obtained caused the waste?s wettability to become an influential parameter in P leaching behavior. The overall conclusion is that kinetic data analysis provides valuable information concerning the sorption mechanism that can be used for predicting the large-scale behavior of soil systems.

Efficiency and environmental indexes to evaluate the sustainability of mineral and organic fertilization in an irrigated melon crop

Melon is traditionally cultivated in fertigated farmlands in the center of Spain with high inputs of water and N fertilizer. Excess N can have a negative impact, from the economic point of view, since it can diminish the production and quality of the fruit, from the environmental point of view, since it is a very mobile element in the soil and can contaminate groundwater. From health point of view, nitrate can be accumulated in fruit pulp, and, in addition, groundwater is the fundamental supply source of human populations. Best management practices are particularly necessary in this region as many zones have been declared vulnerable to NO3- pollution (Directive 91/676/CEE) During successive years, a melon crop (Cucumis melo L.) was grown under field conditions applying mineral and organic fertilizers under drip irrigation. Different doses of ammonium nitrate were used as well as compost derived from the wine-distillery industry which is relevant in this area. The present study reviews the most common N efficiency indexes under the different management options with a view to maximizing yield and minimizing N loss.

Yield, nutrient utilization and soil properties in a melon crop amended with wine-distillery waste

In Spain, large quantities of wine are produced every year (3,339,700 tonnes in 2011) (FAO, 2011) with the consequent waste generation. During the winemaking process, solid residues like grape stalks are generated, as well as grape marc and wine lees as by-products. According to the Council Regulation (EC) 1493/1999 on the common organization of the wine market, by-products coming from the winery industry must be sent to alcohol-distilleries to generate exhausted grape marc and vinasses. With an adequate composting treatment, these wastes can be applied to soils as a source of nutrients and organic matter. A three-year field experiment (2011, 2012 and 2013) was carried out in Ciudad Real (central Spain) to study the effects of wine-distillery waste compost application in a melon crop (Cucumis melo L.). Melon crop has been traditionally cultivated in this area with high inputs of water and fertilizers, but no antecedents of application of winery wastes are known. In a randomized complete block design, four treatments were compared: three compost doses consisted of 6.7 (D1), 13.3 (D2) and 20 t compost ha-1 (D3), and a control treatment without compost addition (D0). The soil was a shallow sandy-loam (Petrocalcic Palexeralfs) with a depth of 0.60 m and a discontinuous petrocalcic horizon between 0.60 and 0.70 m, slightly basic (pH 8.4), poor in organic matter (0.24%), rich in potassium (410 ppm) and with a medium level of phosphorus (22.1 ppm). During each growing period four harvests were carried out and total and marketable yield (fruits weighting <1 kg or visually rotten were not considered), fruit average weight and fruit number per plant were determined. At the end of the crop cycle, four plants per treatment were sampled and the nutrient content (N, P and K) was determined. Soil samplings (0-30 cm depth) were carried before the application of compost and at the end of each growing season and available N and P, as well as exchangeable K content were analyzed. With this information, an integrated analysis was carried out with the aim to evaluate the suitability of this compost as organic amendment.

Water and nitrogen footprint in an irrigated crop under mineral and organic fertilization

In order to establish rational nitrogen (N) application and reduce groundwater contamination, a clearer understanding of the N distribution through the growing season and its balance is crucial. Excessive doses of N and/or water applied to fertigated crops involve a substantial risk of aquifer contamination by nitrate; but knowledge of N cycling and availability within the soil could assist in avoiding this excess. In central Spain, the main horticultural fertigated crop is the melon type ?piel de sapo¿ and it is cultivated in vulnerable zones to nitrate pollution (Directive 91/676/CEE). However, until few years ago there were not antecedents related to the optimization of nitrogen fertilization together with irrigation. Water and N footprint are indicators that allow assessing the impact generated by different agricultural practices, so they can be used to improve the management strategies in fertigated crop systems. The water footprint distinguishes between blue water (sources of water applied to the crop, like irrigation and precipitation), green water (water used by the crop and stored in the soil), and it is furthermore possible to quantify the impact of pollution by calculating the grey water, which is defined as the volume of polluted water created from the growing and production of crops. On the other hand, the N footprint considers green N (nitrogen consumed by the crops and stored in the soil), blue N (N available for crop, like N applied with mineral and/or organic fertilizers, N applied with irrigation water and N mineralized during the crop period), whereas grey N is the amount of N-NO3- washed from the soil to the aquifer. All these components are expressed as the ratio between the components of water or N footprint and the yield (m3 t-1 or kg N t-1 respectively). The objetives of this work were to evaluate the impact derivated from the use of different fertilizer practices in a melon crop using water and N footprint.

Agricultural use of organic wastes as source of nitrogen and phosphorus: risks and opportunities

El nitrógeno (N) y el fósforo (P) son nutrientes esenciales en la producción de cultivos. El desarrollo de los fertilizantes de síntesis durante el siglo XX permitió una intensificación de la agricultura y un aumento de las producciones pero a su vez el gran input de nutrientes ha resultado en algunos casos en sistemas poco eficientes incrementando las pérdidas de estos nutrientes al medio ambiente. En el caso del P, este problema se agrava debido a la escasez de reservas de roca fosfórica necesaria para la fabricación de fertilizantes fosfatados. La utilización de residuos orgánicos en agricultura como fuente de N y P es una buena opción de manejo que permite valorizar la gran cantidad de residuos que se generan. Sin embargo, es importante conocer los procesos que se producen en el suelo tras la aplicación de los mismos, ya que influyen en la disponibilidad de nutrientes que pueden ser utilizados por el cultivo así como en las pérdidas de nutrientes de los agrosistemas que pueden ocasionar problemas de contaminación. Aunque la dinámica del N en el suelo ha sido más estudiada que la del P, los problemas importantes de contaminación por nitratos en zonas vulnerables hacen necesaria la evaluación de aquellas prácticas de manejo que pudieran agravar esta situación, y en el caso de los residuos orgánicos, la evaluación de la respuesta agronómica y medioambiental de la aplicación de materiales con un alto contenido en N (como los residuos procedentes de la industria vinícola y alcoholera). En cuanto al P, debido a la mayor complejidad de su ciclo y de las reacciones que ocurren en el suelo, hay un mayor desconocimiento de los factores que influyen en su dinámica en los sistemas suelo-planta, lo que supone nuevas oportunidades de estudio en la evaluación del uso agrícola de los residuos orgánicos. Teniendo en cuenta los conocimientos previos sobre cada nutriente así como las necesidades específicas en el estudio de los mismos, en esta Tesis se han evaluado: (1) el efecto de la aplicación de residuos procedentes de la industria vinícola y alcoholera en la dinámica del N desde el punto de vista agronómico y medioambiental en una zona vulnerable a la contaminación por nitratos; y (2) los factores que influyen en la disponibilidad de P en el suelo tras la aplicación de residuos orgánicos. Para ello se han llevado a cabo incubaciones de laboratorio así como ensayos de campo que permitieran evaluar la dinámica de estos nutrientes en condiciones reales. Las incubaciones de suelo en condiciones controladas de humedad y temperatura para determinar el N mineralizado se utilizan habitualmente para estimar la disponibilidad de N para el cultivo así como el riesgo medioambiental. Por ello se llevó a cabo una incubación en laboratorio para conocer la velocidad de mineralización de N de un compost obtenido a partir de residuos de la industria vinícola y alcoholera, ampliamente distribuida en Castilla-La Mancha, región con problemas importantes de contaminación de acuíferos por nitratos. Se probaron tres dosis crecientes de compost correspondientes a 230, 460 y 690 kg de N total por hectárea que se mezclaron con un suelo franco arcillo arenoso de la zona. La evolución del N mineral en el suelo a lo largo del tiempo se ajustó a un modelo de regresión no lineal, obteniendo valores bajos de N potencialmente mineralizable y bajas contantes de mineralización, lo que indica que se trata de un material resistente a la mineralización y con una lenta liberación de N en el suelo, mineralizándose tan solo 1.61, 1.33 y 1.21% del N total aplicado con cada dosis creciente de compost (para un periodo de seis meses). Por otra parte, la mineralización de N tras la aplicación de este material también se evaluó en condiciones de campo, mediante la elaboración de un balance de N durante dos ciclos de cultivo (2011 y 2012) de melón bajo riego por goteo, cultivo y manejo agrícola muy característicos de la zona de estudio. Las constantes de mineralización obtenidas en el laboratorio se ajustaron a las temperaturas reales en campo para predecir el N mineralizado en campo durante el ciclo de cultivo del melón, sin embargo este modelo generalmente sobreestimaba el N mineralizado observado en campo, por la influencia de otros factores no tenidos en cuenta para obtener esta predicción, como el N acumulado en el suelo, el efecto de la planta o las fluctuaciones de temperatura y humedad. Tanto el ajuste de los datos del laboratorio al modelo de mineralización como las predicciones del mismo fueron mejores cuando se consideraba el efecto de la mezcla suelo-compost que cuando se aislaba el N mineralizado del compost, mostrando la importancia del efecto del suelo en la mineralización del N procedente de residuos orgánicos. Dado que esta zona de estudio ha sido declarada vulnerable a la contaminación por nitratos y cuenta con diferentes unidades hidrológicas protegidas, en el mismo ensayo de campo con melón bajo riego por goteo se evaluó el riesgo de contaminación por nitratos tras la aplicación de diferentes dosis de compost bajo dos regímenes de riego, riego ajustado a las necesidades del cultivo (90 ó 100% de la evapotranspiración del cultivo (ETc)) o riego excedentario (120% ETc). A lo largo del ciclo de cultivo se estimó semanalmente el drenaje mediante la realización de un balance hídrico, así como se tomaron muestras de la solución de suelo y se determinó su concentración de nitratos. Para evaluar el riesgo de contaminación de las aguas subterráneas asociado con estas prácticas, se utilizaron algunos índices medioambientales para determinar la variación en la calidad del agua potable (Índice de Impacto (II)) y en la concentración de nitratos del acuífero (Índice de Impacto Ambiental (EII)). Para combinar parámetros medioambientales con parámetros de producción, se calculó la eficiencia de manejo. Se observó que la aplicación de compost bajo un régimen de riego ajustado no aumentaba el riesgo de contaminación de las aguas subterráneas incluso con la aplicación de la dosis más alta. Sin embargo, la aplicación de grandes cantidades de compost combinada con un riego excedentario supuso un incremento en el N lixiviado a lo largo del ciclo de cultivo, mientras que no se obtuvieron mayores producciones con respecto al riego ajustado. La aplicación de residuos de la industria vinícola y alcoholera como fuente de P fue evaluada en suelos calizos caracterizados por una alta capacidad de retención de P, lo cual en algunos casos limita la disponibilidad de este nutriente. Para ello se llevó a cabo otro ensayo de incubación con dos suelos de diferente textura, con diferente contenido de carbonato cálcico, hierro y con dos niveles de P disponible; a los que se aplicaron diferentes materiales procedentes de estas industrias (con y sin compostaje previo) aportando diferentes cantidades de P. A lo largo del tiempo se analizó el P disponible del suelo (P Olsen) así como el pH y el carbono orgánico disuelto. Al final de la incubación, con el fin de estudiar los cambios producidos por los diferentes residuos en el estado del P del suelo se llevó a cabo un fraccionamiento del P inorgánico del suelo, el cual se separó en P soluble y débilmente enlazado (NaOH-NaCl-P), P soluble en reductores u ocluido en los óxidos de Fe (CBD-P) y P poco soluble precipitado como Ca-P (HCl-P); y se determinó la capacidad de retención de P así como el grado de saturación de este elemento en el suelo. En este ensayo se observó que, dada la naturaleza caliza de los suelos, la influencia de la cantidad de P aplicado con los residuos en el P disponible sólo se producía al comienzo del periodo de incubación, mientras que al final del ensayo el incremento en el P disponible del suelo se igualaba independientemente del P aplicado con cada residuo, aumentando el P retenido en la fracción menos soluble con el aumento del P aplicado. Por el contrario, la aplicación de materiales orgánicos menos estabilizados y con un menor contenido en P, produjo un aumento en las formas de P más lábiles debido a una disolución del P retenido en la fracción menos lábil, lo cual demostró la influencia de la materia orgánica en los procesos que controlan el P disponible en el suelo. La aplicación de residuos aumentó el grado de saturación de P de los suelos, sin embargo los valores obtenidos no superaron los límites establecidos que indican un riesgo de contaminación de las aguas. La influencia de la aplicación de residuos orgánicos en las formas de P inorgánico y orgánico del suelo se estudió además en un suelo ácido de textura areno francosa tras la aplicación en campo a largo plazo de estiércol vacuno y de compost obtenido a partir de biorresiduos, así como la aplicación combinada de compost y un fertilizante mineral (superfosfato tripe), en una rotación de cultivos. En muestras de suelo recogidas 14 años después del establecimiento del experimento en campo, se determinó el P soluble y disponible, la capacidad de adsorción de P, el grado de saturación de P así como diferentes actividades enzimáticas (actividad deshidrogenasa, fosfatasa ácida y fosfatasa alcalina). Las diferentes formas de P orgánico en el suelo se estudiaron mediante una técnica de adición de enzimas con diferentes substratos específicos a extractos de suelo de NaOH-EDTA, midiendo el P hidrolizado durante un periodo de incubación por colorimetría. Las enzimas utilizadas fueron la fosfatasa ácida, la nucleasa y la fitasa las cuales permitieron identificar monoésteres hidrolizables (monoester-like P), diésteres (DNA-like P) e inositol hexaquifosfato (Ins6P-like P). La aplicación a largo plazo de residuos orgánicos aumentó el P disponible del suelo proporcionalmente al P aplicado con cada tipo de fertilización, suponiendo un mayor riesgo de pérdidas de P dado el alto grado de saturación de este suelo. La aplicación de residuos orgánicos aumentó el P orgánico del suelo resistente a la hidrólisis enzimática, sin embargo no influyó en las diferentes formas de P hidrolizable por las enzimas en comparación con las observadas en el suelo sin enmendar. Además, las diferentes formas de P orgánico aplicadas con los residuos orgánicos no se correspondieron con las analizadas en el suelo lo cual demostró que éstas son el resultado de diferentes procesos en el suelo mediados por las plantas, los microorganismos u otros procesos abióticos. En este estudio se encontró una correlación entre el Ins6P-like P y la actividad microbiana (actividad deshidrogenasa) del suelo, lo cual refuerza esta afirmación. Por último, la aplicación de residuos orgánicos como fuente de N y P en la agricultura se evaluó agronómicamente en un escenario real. Se estableció un experimento de campo para evaluar el compost procedente de residuos de bodegas y alcoholeras en el mismo cultivo de melón utilizado en el estudio de la mineralización y lixiviación de N. En este experimento se estudió la aplicación de tres dosis de compost: 1, 2 y 3 kg de compost por metro lineal de plantación correspondientes a 7, 13 y 20 t de compost por hectárea respectivamente; y se estudió el efecto sobre el crecimiento de las plantas, la acumulación de N y P en la planta, así como la producción y calidad del cultivo. La aplicación del compost produjo un ligero incremento en la biomasa vegetal acompañado por una mejora significativa de la producción con respecto a las parcelas no enmendadas, obteniéndose la máxima producción con la aplicación de 2 kg de compost por metro lineal. Aunque los efectos potenciales del N y P fueron parcialmente enmascarados por otras entradas de estos nutrientes en el sistema (alta concentración de nitratos en el agua de riego y ácido fosfórico suministrado por fertirrigación), se observó una mayor acumulación de P uno de los años de estudio que resultó en un aumento en el número de frutos en las parcelas enmendadas. Además, la mayor acumulación de N y P disponible en el suelo al final del ciclo de cultivo indicó el potencial uso de estos materiales como fuente de estos nutrientes. ABSTRACT Nitrogen (N) and phosphorus (P) are essential nutrients in crop production. The development of synthetic fertilizers during the 20th century allowed an intensification of the agriculture increasing crop yields but in turn the great input of nutrients has resulted in some cases in inefficient systems with higher losses to the environment. Regarding P, the scarcity of phosphate rock reserves necessary for the production of phosphate fertilizers aggravates this problem. The use of organic wastes in agriculture as a source of N and P is a good option of management that allows to value the large amount of wastes generated. However, it is important to understand the processes occurring in the soil after application of these materials, as they affect the availability of nutrients that can be used by the crop and the nutrient losses from agricultural systems that can cause problems of contamination. Although soil N dynamic has been more studied than P, the important concern of nitrate pollution in Nitrate Vulnerable Zones requires the evaluation of those management practices that could aggravate this situation, and in the case of organic wastes, the evaluation of the agronomic and environmental response after application of materials with a high N content (such as wastes from winery and distillery industries). On the other hand, due to the complexity of soil P cycle and the reactions that occur in soil, there is less knowledge about the factors that can influence its dynamics in the soil-plant system, which means new opportunities of study regarding the evaluation of the agricultural use of organic wastes. Taking into account the previous knowledge of each nutrient and the specific needs of study, in this Thesis we have evaluated: (1) the effect of the application of wastes from the winery and distillery industries on N dynamics from the agronomic and environmental viewpoint in a vulnerable zone; and (2) the factors that influence P availability in soils after the application of organic wastes. With this purposes, incubations were carried out in laboratory conditions as well as field trials that allow to assess the dynamic of these nutrients in real conditions. Soil incubations under controlled moisture and temperature conditions to determine N mineralization are commonly used to estimate N availability for crops together with the environmental risk. Therefore, a laboratory incubation was conducted in order to determine the N mineralization rate of a compost made from wastes generated in the winery and distillery industries, widely distributed in Castilla-La Mancha, a region with significant problems of aquifers contamination by nitrates. Three increasing doses of compost corresponding to 230, 460 and 690 kg of total N per hectare were mixed with a sandy clay loam soil collected in this area. The evolution of mineral N in soil over time was adjusted to a nonlinear regression model, obtaining low values of potentially mineralizable N and low constants of mineralization, indicating that it is a material resistant to mineralization with a slow release of N, with only 1.61, 1.33 and 1.21% of total N applied being mineralized with each increasing dose of compost (for a period of six months). Furthermore, N mineralization after the application of this material was also evaluated in field conditions by carrying out a N balance during two growing seasons (2011 and 2012) of a melon crop under drip irrigation, a crop and management very characteristic of the area of study. The mineralization constants obtained in the laboratory were adjusted to the actual temperatures observed in the field to predict N mineralized during each growing season, however, this model generally overestimated the N mineralization observed in the field, because of the influence of other factors not taken into account for this prediction, as N accumulated in soil, the plant effect or the fluctuations of temperature and moisture. The fitting of the laboratory data to the model as well as the predictions of N mineralized in the field were better when considering N mineralized from the soil-compost mixture rather than when N mineralized from compost was isolated, underlining the important role of the soil on N mineralization from organic wastes. Since the area of study was declared vulnerable to nitrate pollution and is situated between different protected hydrological units, the risk of nitrate pollution after application of different doses compost was evaluated in the same field trial with melon under two irrigation regimes, irrigation adjusted to the crop needs (90 or 100% of the crop evapotranspiration (ETc)) or excedentary irrigation (120% ETc). Drainage was estimated weekly throughout the growing season by conducting a water balance, samples of the soil solution were taken and the concentration of nitrates was determined. To assess the risk of groundwater contamination associated with these practices, some environmental indices were used to determine the variation in the quality of drinking water (Impact Index (II)) and the nitrates concentration in the groundwater (Environmental Impact Index (EII)). To combine environmental parameters together with yield parameters, the Management Efficiency was calculated. It was observed that the application of compost under irrigation adjusted to the plant needs did not represent a higher risk of groundwater contamination even with the application of the highest doses. However, the application of large amounts of compost combined with an irrigation surplus represented an increase of N leaching during the growing season compared with the unamended plots, while no additional yield with respect to the adjusted irrigation strategy is obtained. The application of wastes derived from the winery and distillery industry as source of P was evaluated in calcareous soils characterized by a high P retention capacity, which in some cases limits the availability of this nutrient. Another incubation experiment was carried out using two soils with different texture, different calcium carbonate and iron contents and two levels of available P; to which different materials from these industries (with and without composting) were applied providing different amounts of P. Soil available P (Olsen P), pH and dissolved organic carbon were analyzed along time. At the end of the incubation, in order to study the changes in soil P status caused by the different residues, a fractionation of soil inorganic P was carried out, which was separated into soluble and weakly bound P (NaOH-NaCl- P), reductant soluble P or occluded in Fe oxides (CBD-P) and P precipitated as poorly soluble Ca-P (HCl-P); and the P retention capacity and degree of P saturation were determined as well. Given the calcareous nature of the soils, the influence of the amount of P applied with the organic wastes in soil available P only occurred at the beginning of the incubation period, while at the end of the trial the increase in soil available P equalled independently of the amount of P applied with each residue, increasing the P retained in the least soluble fraction when increasing P applied. Conversely, the application of less stabilized materials with a lower content of P resulted in an increase in the most labile P forms due to dissolution of P retained in the less labile fraction, demonstrating the influence of organic matter addition on soil P processes that control P availability in soil. As expected, the application of organic wastes increased the degree of P saturation in the soils, however the values obtained did not exceed the limits considered to pose a risk of water pollution. The influence of the application of organic wastes on inorganic and organic soil P forms was also studied in an acid loamy sand soil after long-term field application of cattle manure and biowaste compost and the combined application of compost and mineral fertilizer (triple superphosphate) in a crop rotation. Soil samples were collected 14 years after the establishment of the field experiment, and analyzed for soluble and available P, P sorption capacity, degree of P saturation and enzymatic activities (dehydrogenase, acid phosphatase and alkaline phosphatase). The different forms of organic P in soil were determined by using an enzyme addition technique, based on adding enzymes with different substrate specificities to NaOH-EDTA soil extracts, measuring the hydrolyzed P colorimetrically after an incubation period. The enzymes used were acid phosphatase, nuclease and phytase which allowed to identify hydrolyzable monoesters (monoester-like P) diesters (DNA-like P) and inositol hexakisphosphate (Ins6P-like P). The long-term application of organic wastes increased soil available P proportionally to the P applied with each type of fertilizer, assuming a higher risk of P losses given the high degree of P saturation of this soil. The application of organic wastes increased soil organic P resistant to enzymatic hydrolysis, but no influence was observed regarding the different forms of enzyme hydrolyzable organic P compared to those observed in the non-amended soil. Furthermore, the different forms of organic P applied with the organic wastes did not correspond to those analyzed in the soil which showed that these forms in soil are a result of multifaceted P turnover processes in soil affected by plants, microorganisms and abiotic factors. In this study, a correlation between Ins6P-like P and the microbial activity (dehydrogenase activity) of soil was found, which reinforces this claim. Finally, the application of organic wastes as a source of N and P in agriculture was evaluated agronomically in a real field scenario. A field experiment was established to evaluate the application of compost made from wine-distillery wastes in the same melon crop used in the experiments of N mineralization and leaching. In this experiment the application of three doses of compost were studied: 1 , 2 and 3 kg of compost per linear meter of plantation corresponding to 7, 13 and 20 tonnes of compost per hectare respectively; and the effect on plant growth, N and P accumulation in the plant as well as crop yield and quality was studied. The application of compost produced a slight increase in plant biomass accompanied by a significant improvement in crop yield with respect to the unamended plots, obtaining the maximum yield with the application of 2 kg of compost per linear meter. Although the potential effects of N and P were partially masked by other inputs of these nutrients in the system (high concentration of nitrates in the irrigation water and phosphoric acid supplied by fertigation), an effect of P was observed the first year of study resulting in a greater plant P accumulation and in an increase in the number of fruits in the amended plots. In addition, the higher accumulation of available N and P in the topsoil at the end of the growing season indicated the potential use of this material as source of these nutrients.

Heterogeneous catalysts for environmentally sustainable reactions

This PhD work deals with problems of synthetic organic chemistry with particular attention to the development of environmentally friendly processes. In particular, new synthetic strategies have been studied based on the use of low cost heterogeneous catalysts, non-toxic reagents and mild operating conditions that do not involve, when possible, the use of solvents. The catalysts examined are both basic and acids, commercial or prepared by hetereogenization of homogeneous catalysts synthesized by tethering or impregnation. In particular it will be discussed the catalytic activity of oxides (Al2O3 and TiO2), supported sulphonic acids and hydrotalcites for the reactions of selective monoesterificazion of dicarboxylic acids, dehydrogenation of butane in gas phase, esterification of levulinic acid, Friedel-Craft acylations, C-C and C-P coupling. The use of these materials has allowed the development of simple processes with low environmental impact. The operating conditions are in fact mild and reaction times short. The selectivity for the desired products is in all reported cases very high and the catalysts can be recycled maintaining their optimum performances.

Efeito da aplicação de composto orgânico sobre a qualidade do solo cultivado com cana-de-açúcar (Saccharum spp.)

A dinâmica ambiental possui capacidade limitada de reciclagem e a crescente utilização resíduos agroindustriais, especialmente na agricultura, pode levar a situações de poluição do solo e demais componentes ambientais. A manutenção da produtividade de ecossistemas agrícolas e naturais depende do processo de transformação da matéria orgânica e, por conseguinte, da biomassa microbiana do solo, e que é responsável pela decomposição e mineralização de resíduos no mesmo. A dinâmica natural dos microrganismos do solo, em constante mudança e adaptação, os torna um indicador sensível às mudanças resultantes de diferentes práticas de manejo agrícola. Sendo assim, conhecer essas alterações e suas interferências é fundamental para identificar estratégias adequadas de manejo, apontando técnicas de utilização adequadas. O objetivo deste trabalho foi avaliar a qualidade de um solo agrícola, cultivado com três variedades de cana-de-açúcar (Saccharum spp.), comparando a utilização de adubação mineral frente à utilização de fertilizante orgânico composto no período final de formação dos perfilhos (120 dias após o plantio). Foi implantado, em condições de campo, o cultivo de cana-de-açúcar (cana planta), utilizando as variedades RB 867515, RB 962869 e RB 855453, onde cada variedade foi cultivada de três formas distintas, sendo elas: plantio controle (CT) sem aplicação de insumos para adubação; plantio orgânico (OG) com aplicação de fertilizante orgânico; e plantio convencional (CV) com aplicação de adubação mineral, seguindo recomendações de adubação após análise química inicial do solo local. Cada parcela possuía 37 m2, com 5 sulcos de 5,0 m de comprimento e espaçamento de 1,5 m entrelinhas, sendo os três sulcos centrais formando a área útil. De acordo com a variedade e o tipo de adubação, foram formados nove tratamentos: T1 86CT, T2 96CT, T3 85CT, T4 6OG, T5 96OG, T6 85OG, T7 86CV, T8 96CV e T9 85CV, com delineamento estatístico de blocos ao acaso e quatro repetições. Os parâmetros químicos do solo analisados foram macronutrientes e micronutrientes; os parâmetros microbiológicos foram carbono da biomassa microbiana (CBM), respiração basal do solo (RBS), quociente metabólico (qCO2), número mais provável de fungos e bactérias do solo (NMP); e, por fim, a produtividade agrícola (t/ha). Os resultados foram submetidos a análise de variância (ANOVA) e à comparação das médias através do teste de Tukey (10%). Também foi realizada a análise de variância dos dados e correlação cofenética de Pearson para formação de dendogramas. Com base no período estudado, considerado como fase crítica da formação do canavial, concluiu-se que os parâmetros químicos que evidenciaram alterações no solo foram pH e os macronutrientes Mg, Al e SB, sendo os tratamentos orgânicos equivalentes e/ou melhores que os tratamentos convencionais. Para os parâmetros microbiológicos, o NMP de fungos apresentou os maiores valores nos tratamentos convencionais e controle. A produtividade agrícola não foi influenciada pelos diferentes tratamentos e insumos utilizados, independente da variedade de cana-de-açúcar utilizada. Por fim, foram observadas correlações positivas entre as variáveis CTC e quociente metabólico (qCO2) apontando potencial melhoria da qualidade do solo, com o emprego de insumos orgânicos

A Community Analysis of the Implementation for Household Curbside Recycling Programs: A Diversionary Method to Control Municipal Solid Waste

The Municipality of Anchorage (MOA) is required to better manage, operate and control municipal solid waste (MSW) after the Anchorage Assembly instituted a Zero Waste Policy. Two household curbside recycling programs (CRPs), pay-as-you-throw (PAYT) and single-stream, were compared and evaluated to determine an optimal municipal solid waste diversion method for households within the MOA. The analyses find: (1) a CRP must be designed from comprehensive analysis, models and data correlation that combine demographic and psychographic variables; and (2) CRPs can be easily adjusted towards community-specific goals using technology, such as Geographic Information System (GIS) and Radio Frequency Identification (RFID). Combining resources of policy-makers, businesses, and other viable actors are necessary components to produce a sustainable, economically viable curbside recycling program.

Integration of Sustainable Development Principles into a Community Park

Characteristics of six operating hot spring recreational facilities were reviewed to identify opportunities for integrating a range of sustainable design and operation approaches into a community park. Potential operating cost savings were evaluated for a conceptual landscape project, bathhouse project, and swimming pool project that reduced the use of electricity, natural gas, water, the discharge of water, and solid waste generation. The projects showed a combined cost savings of approximately $40,000 per year by adopting passive solar design, energy efficient lighting, native vegetation, water efficient fixtures, and a natural swimming pool. The greatest potential operating cost reductions were observed for cutbacks in the use of swimming pool water and reductions in natural gas needed for building and swimming pool heating.

Comparative Evaluation of Groundwater Management Practices of the Ogallala Aquifer

Mining of groundwater, or extracting a larger quantity of water than what is naturally returned to the aquifer through recharge, has been occurring for more than fifty years. The minimal natural recharge to the Ogallala Aquifer makes sustainable use of this resource a daunting task for states across the High Plains that rely on it to support their well-established ways of life. This task is compounded when considering the different combinations of federal, state and local governance, as well as regional economic and social frameworks that each state overlaying the aquifer experiences. This project critically examines factors contributing to groundwater management successes and failures of three states that overlay the majority (87%) of this resource: Nebraska, Kansas and Texas.