Modelos predictivos y preventivos para una Administración Pública sostenible

Con la finalidad de ayudar a la creación y desarrollo de modelos de predicción y simulación que permitan al ciudadano/administraciones publicas gestionar el consumo energético de forma más eficiente y respetuosa con el medio ambiente, se ha implementado un sistema de gestión de datos de indicadores energéticos. En 2007 la UE creó una directiva conocida como "20/20/20" en la que la Unión Europea se compromete a ahorrar un 20% del consumo anual de energía primaria desde esa fecha a 2020. En 2009 la Comisión Europea ha llegado a la conclusión de que con las medidas propuestas en dicha directiva no se podría alcanzar el objetivo de reducción del 20% del consumo energético previsto para el 2020, quedándose en menos de la mitad. Para dar un nuevo impulso a la eficiencia energética se redacta una propuesta de directiva: 2011/0172(COD). En esta directiva se obliga a los estados miembros a potenciar y ampliar la información estadística agregada sobre sus clientes finales (los perfiles de carga, la segmentación de los clientes, su ubicación geográfica, etc ). La Unión Europea plantea que incrementar el volumen y la accesibilidad de los datos de consumo energético, ayudará de forma significativa a alcanzar los objetivos. En este marco, parece lógico afirmar que un banco de datos de indicadores energéticos universalmente accesible puede contribuir de un modo efectivo al aumento de la eficiencia energética. Como aplicativo de este PFC se ha desarrollado una aplicación que permite la definición y almacenamiento de indicadores energéticos, en la que los diferentes sistemas, propietarios o abiertos, pueden volcar y extraer datos de una forma poco costosa. Se ha pretendido realizar una aplicación lo más abierta posible, tanto desde el punto de vista de la funcionalidad, permitiendo la definición del propio indicador a través del sistema, como desde el punto de vista de la implementación, usando únicamente código abierto para el desarrollo de la misma. ABSTRACT. In order to assist in the creation and development of forecasting and simulation models that enable citizens / public authorities manage energy consumption more efficient and environmentally friendly, we have implemented a data management system of energy indicators. In 2007 the EU created a policy known as " 20/20/20 " in which the European Union is committed to saving 20 % of the annual primary energy consumption from that date to 2020 . In 2009 the European Commission has concluded that the measures proposed in the directive could not achieve the goal of 20% reduction in energy consumption expected for 2020 , staying in less than half. To give new impetus to energy efficiency is drawn up a draft directive : 2011/0172 ( COD ) . This directive obliges member states to strengthen and expand aggregate statistical information on their final customers ( load profiles , customer segmentation , geographic location, etc. ) . The European Union argues that increasing the volume and accessibility ofenergy data , will significantly help to achieve the objectives . In this context , it seems logical to say that a database of universally accessible energy indicators can contribute in an effective way to increase energy efficiency. As of this PFC application has developed an application that allows the definition and storage of energy indicators , in which different systems, proprietary or open, can tip and extract data from an inexpensive way. We have tried to make an application as open as possible , both from the point of view of functionality , allowing the definition of the indicator itself through the system , and from the point of view of implementation, using only open source development thereof.

Localization and Tracking in Energy-Constrained Networks with Dynamic Connectivity

Systems used for target localization, such as goods, individuals, or animals, commonly rely on operational means to meet the final application demands. However, what would happen if some means were powered up randomly by harvesting systems? And what if those devices not randomly powered had their duty cycles restricted? Under what conditions would such an operation be tolerable in localization services? What if the references provided by nodes in a tracking problem were distorted? Moreover, there is an underlying topic common to the previous questions regarding the transfer of conceptual models to reality in field tests: what challenges are faced upon deploying a localization network that integrates energy harvesting modules? The application scenario of the system studied is a traditional herding environment of semi domesticated reindeer (Rangifer tarandus tarandus) in northern Scandinavia. In these conditions, information on approximate locations of reindeer is as important as environmental preservation. Herders also need cost-effective devices capable of operating unattended in, sometimes, extreme weather conditions. The analyses developed are worthy not only for the specific application environment presented, but also because they may serve as an approach to performance of navigation systems in absence of reasonably accurate references like the ones of the Global Positioning System (GPS). A number of energy-harvesting solutions, like thermal and radio-frequency harvesting, do not commonly provide power beyond one milliwatt. When they do, battery buffers may be needed (as it happens with solar energy) which may raise costs and make systems more dependent on environmental temperatures. In general, given our problem, a harvesting system is needed that be capable of providing energy bursts of, at least, some milliwatts. Many works on localization problems assume that devices have certain capabilities to determine unknown locations based on range-based techniques or fingerprinting which cannot be assumed in the approach considered herein. The system presented is akin to range-free techniques, but goes to the extent of considering very low node densities: most range-free techniques are, therefore, not applicable. Animal localization, in particular, uses to be supported by accurate devices such as GPS collars which deplete batteries in, maximum, a few days. Such short-life solutions are not particularly desirable in the framework considered. In tracking, the challenge may times addressed aims at attaining high precision levels from complex reliable hardware and thorough processing techniques. One of the challenges in this Thesis is the use of equipment with just part of its facilities in permanent operation, which may yield high input noise levels in the form of distorted reference points. The solution presented integrates a kinetic harvesting module in some nodes which are expected to be a majority in the network. These modules are capable of providing power bursts of some milliwatts which suffice to meet node energy demands. The usage of harvesting modules in the aforementioned conditions makes the system less dependent on environmental temperatures as no batteries are used in nodes with harvesters--it may be also an advantage in economic terms. There is a second kind of nodes. They are battery powered (without kinetic energy harvesters), and are, therefore, dependent on temperature and battery replacements. In addition, their operation is constrained by duty cycles in order to extend node lifetime and, consequently, their autonomy. There is, in turn, a third type of nodes (hotspots) which can be static or mobile. They are also battery-powered, and are used to retrieve information from the network so that it is presented to users. The system operational chain starts at the kinetic-powered nodes broadcasting their own identifier. If an identifier is received at a battery-powered node, the latter stores it for its records. Later, as the recording node meets a hotspot, its full record of detections is transferred to the hotspot. Every detection registry comprises, at least, a node identifier and the position read from its GPS module by the battery-operated node previously to detection. The characteristics of the system presented make the aforementioned operation own certain particularities which are also studied. First, identifier transmissions are random as they depend on movements at kinetic modules--reindeer movements in our application. Not every movement suffices since it must overcome a certain energy threshold. Second, identifier transmissions may not be heard unless there is a battery-powered node in the surroundings. Third, battery-powered nodes do not poll continuously their GPS module, hence localization errors rise even more. Let's recall at this point that such behavior is tight to the aforementioned power saving policies to extend node lifetime. Last, some time is elapsed between the instant an identifier random transmission is detected and the moment the user is aware of such a detection: it takes some time to find a hotspot. Tracking is posed as a problem of a single kinetically-powered target and a population of battery-operated nodes with higher densities than before in localization. Since the latter provide their approximate positions as reference locations, the study is again focused on assessing the impact of such distorted references on performance. Unlike in localization, distance-estimation capabilities based on signal parameters are assumed in this problem. Three variants of the Kalman filter family are applied in this context: the regular Kalman filter, the alpha-beta filter, and the unscented Kalman filter. The study enclosed hereafter comprises both field tests and simulations. Field tests were used mainly to assess the challenges related to power supply and operation in extreme conditions as well as to model nodes and some aspects of their operation in the application scenario. These models are the basics of the simulations developed later. The overall system performance is analyzed according to three metrics: number of detections per kinetic node, accuracy, and latency. The links between these metrics and the operational conditions are also discussed and characterized statistically. Subsequently, such statistical characterization is used to forecast performance figures given specific operational parameters. In tracking, also studied via simulations, nonlinear relationships are found between accuracy and duty cycles and cluster sizes of battery-operated nodes. The solution presented may be more complex in terms of network structure than existing solutions based on GPS collars. However, its main gain lies on taking advantage of users' error tolerance to reduce costs and become more environmentally friendly by diminishing the potential amount of batteries that can be lost. Whether it is applicable or not depends ultimately on the conditions and requirements imposed by users' needs and operational environments, which is, as it has been explained, one of the topics of this Thesis.

Polypropylene/glass fiber hierarchical composites incorporating inorganic fullerene-like nanoparticles for advanced technological applications

Novel isotactic polypropylene (iPP)/glass fiber (GF) laminates reinforced with inorganic fullerene-like tungsten disulfide (IF-WS2) nanoparticles as environmentally friendly fillers have been successfully fabricated by simple melt-blending and fiber impregnation in a hot-press without the addition of any compatibilizer. The influence of IF-WS2 concentration on the morphology, viscosity. and thermal and mechanical behavior of the hierarchical composites has been investigated. Results revealed an unprecedented 62 °C increase in the degradation temperature of iPP/GF upon addition of only 4.0 wt % IF-WS2. The coexistence of both micro- and nanoscale fillers resulted in synergistic effects on enhancing the stiffness, strength, crystallinity, thermal stability, glass transition (Tg) and heat distortion temperature (HDT) of the matrix. The approach used in this work is an efficient, versatile, scalable and economic strategy to improve the mechanical and thermal behavior of GF-reinforced thermoplastics with a view to extend their use in advanced technological applications. This new type of composite materials shows great potential to improve the efficiency and sustainability of many forms of transport.

Opportunities and challenges in the use of inorganic fullerene-like nanoparticles to produce advanced polymer nanocomposites

Polymer/inorganic nanoparticle nanocomposites have garnered considerable academic and industrial interest over recent decades in the development of advanced materials for a wide range of applications. In this respect, the dispersion of so-called inorganic fullerene-like (IF) nanoparticles, e.g., tungsten disulfide (IF-WS2) or molybdenum disulfide (IF-MoS2), into polymeric matrices is emerging as a new strategy. The surprising properties of these layered metal dichalcogenides such as high impact resistance and superior tribological behavior, attributed to their nanoscale size and hollow quasi-spherical shape, open up a wide variety of opportunities for applications of these inorganic compounds. The present work presents a detailed overview on research in the area of IF-based polymer nanocomposites, with special emphasis on the use of IF-WS2 nanoparticles as environmentally friendly reinforcing fillers. The incorporation of IF particles has been shown to be efficient for improving thermal, mechanical and tribological properties of various thermoplastic polymers, such as polypropylene, nylon-6, poly(phenylene sulfide), poly(ether ether ketone), where nanocomposites were fabricated by simple melt-processing routes without the need for modifiers or surfactants. This new family of nanocomposites exhibits similar or enhanced performance when compared with nanocomposites that incorporate carbon nanotubes, carbon nanofibers or nanoclays, but are substantially more cost-effective, efficient and environmentally satisfactory. Most recently, innovative approaches have been described that exploit synergistic effects to produce new materials with enhanced properties, including the combined use of micro- and nanoparticles such as IF-WS2/nucleating agent or IF-WS2/carbon fiber, as well as dual nanoparticle systems such as SWCNT/IF-WS2 where each nanoparticle has different characteristics. The structure–property relationships of these nanocomposites are discussed and potential applications proposed ranging from medicine to the aerospace, automotive and electronics industries.

Mulch materials in processing tomato: a multivariate approach.

Mulch materials of different origins have been introduced into the agricultural sector in recent years alternatively to the standard polyethylene due to its environmental impact. This study aimed to evaluate the multivariate response of mulch materials over three consecutive years in a processing tomato (Solanum lycopersicon L.) crop in Central Spain. Two biodegradable plastic mulches (BD1, BD2), one oxo-biodegradable material (OB), two types of paper (PP1, PP2), and one barley straw cover (BS) were compared using two control treatments (standard black polyethylene [PE] and manual weed control [MW]). A total of 17 variables relating to yield, fruit quality, and weed control were investigated. Several multivariate statistical techniques were applied, including principal component analysis, cluster analysis, and discriminant analysis. A group of mulch materials comprised of OB and BD2 was found to be comparable to black polyethylene regarding all the variables considered. The weed control variables were found to be an important source of discrimination. The two paper mulches tested did not share the same treatment group membership in any case: PP2 presented a multivariate response more similar to the biodegradable plastics, while PP1 was more similar to BS and MW. Based on our multivariate approach, the materials OB and BD2 can be used as an effective, more environmentally friendly alternative to polyethylene mulches.

Long Term Performance Study of a Direct Methanol Fuel Cell Fed with Alcohol Blends

The use of alcohol blends in direct alcohol fuel cells may be a more environmentally friendly and less toxic alternative to the use of methanol alone in direct methanol fuel cells. This paper assesses the behaviour of a direct methanol fuel cell fed with aqueous methanol, aqueous ethanol and aqueous methanol/ethanol blends in a long term experimental study followed by modelling of polarization curves. Fuel cell performance is seen to decrease as the ethanol content rises, and subsequent operation with aqueous methanol only partly reverts this loss of performance. It seems that the difference in the oxidation rate of these alcohols may not be the only factor affecting fuel cell performance.

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.

Sistema de descarga para metaneros de hasta 145000 m3 con gasinera para buques a propulsión de GNL

Current social demand for more environmentally-friendly fuels environment has imposed stringent emissions standards infectious greenhouse affecting all means of transport, including maritime. A few free zones emissions (ECA) in waters around the world have been established. This has driven to the Liquefied Natural Gas (LNG) as the fuel of the future for ships to comply with emissions laid down by the Convention International Prevention of the Pollution from Ships (MARPOL). The present work proposes the installation of a LNG station for ships in the future regasification plant of Granadilla (Santa Cruz de Tenerife). The work has understood the design and sizing of the receiving of the regasification plant terminal pipelines, as well as pipes for the LNG station. La demanda social actual por combustibles más respetuosos con el medio ambiente ha impuesto unas estrictas normas de emisiones de gases infecto invernadero que afectan a todos los medios de transporte, incluido el marítimo. Se han establecido unas zonas libres de emisiones (ECA) en aguas de todo el mundo. Esto ha impulsado al Gas Natural Licuado (GNL) como el combustible del futuro para buques para cumplir con las emisiones fijadas por la Convención Internacional de Prevención de la Contaminación de Barcos (MARPOL). El presente trabajo propone la instalación de una gasinera para buques en la futura planta de regasificación de Granadilla (Santa Cruz de Tenerife). El trabajo ha comprendido el diseño y dimensionamiento de las tuberías de la terminal de recepción de la planta de regasificación, así como las tuberías para la gasinera.

Novel poly(3-hydroxybutyrate) nanocomposites containing WS2 inorganic nanotubes with improved thermal, mechanical and tribological properties

Poly(3-hydroxybutyrate) (PHB) nanocomposites containing environmentally-friendly tungsten disulphide inorganic nanotubes (INTeWS2) have been successfully prepared by a simple solution blending method. The dynamic and isothermal crystallization studies by differential scanning calorimetry (DSC) demonstrated that the INTeWS2 exhibits much more prominent nucleation activity on the crystallization of PHB than specific nucleating agents or other nanoscale fillers. Both crystallization rate and crystallinity significantly increase in the nanocomposites compared to neat PHB. These changes occur without modifying the crystalline structure of PHB in the nanocomposites, as shown by wide-angle X-ray diffraction (WAXS) and infrared/Raman spectroscopy. Other parameters such as the Avrami exponent, the equilibrium melting temperature, global rate constant and the fold surface free energy of PHB chains in the nanocomposites were obtained from the calorimetric data in order to determine the influence of the INTeWS2 filler. The addition of INTeWS2 remarkably influences the energetics and kinetics of nucleation and growth of PHB, reducing the fold surface free energy by up to 20%. Furthermore, these nanocomposites also show an improvement in both tribological and mechanical (hardness and modulus) properties with respect to pure PHB evidenced by friction and nanoindentation tests, which is of important potential interest for industrial and medical applications.

Contêineres metálicos para canteiros de obras: análise experimental de desempenho térmico e melhorias na transferência de calor pela envoltória.

Os contêineres metálicos foram desenvolvidos para a utilização no setor de logística e transporte, mas por sua escala adaptável à das edificações e pela mobilidade e praticidade de instalação, tiveram sua utilização apropriada também pelo setor da construção civil. Essas instalações possuem diversas qualidades ambientalmente amigáveis, mas seu aspecto térmico é extremamente insuficiente: sem isolamento térmico, demandam alta carga térmica de refrigeração e aquecimento, no verão e inverno, respectivamente e, consequentemente, um alto consumo energético. Tal característica foi crucial para que se determinassem como objetivos da presente pesquisa investigar o comportamento térmico dessas construções metálicas, avaliar seus parâmetros de desempenho, conforto e estresse térmicos, por meio de uma ampla coleta de dados experimentais. O experimento com duração de um ano - contou com três tipologias de contêiner em escala real, sendo o primeiro em aço Tipo X sem isolamento térmico, o segundo com um isolamento térmico para o fenômeno da condução e o terceiro com isolamento térmico para o fenômeno da radiação. Os diferentes tipos de tratamentos térmicos proporcionaram melhorias à envoltória dos contêineres, chegando a uma diferença nas temperaturas internas de até 9 °C. Constatou-se a extrema necessidade de adequação do tipo de isolamento térmico dos contêineres ao uso a que tais instalações se destinam escritório ou alojamento, no caso dos canteiros de obras para que as características da envoltória minimizem de fato a demanda ou mesmo atinjam a eliminação da necessidade de condicionamento artificial.

Efeito da adição de fibras de cana-de-açúcar pré-tratadas na produção de metano advinda da biodigestão anaeróbia de gorduras do leite

A digestão anaeróbia é uma alternativa para o tratamento de resíduos com altas concentrações de matéria orgânica. Por meio dos processos anaeróbios é possível a produção de biogás, fonte de energia renovável e ambientalmente amigável. Elevadas concentrações de lipídios, todavia, apesar de representarem elevado potencial metanogênico, interferem negativamente nos sistemas de tratamento, podendo inibir a atividade microbiana e, consequentemente, a produção de metano. O presente projeto avaliou o efeito da adição de bagaço de cana-de-açúcar no processo de biodigestão anaeróbia de elevadas concentrações de gorduras advindas de efluentes de laticínio. Para tanto foi utilizado bagaço de cana-de-açúcar in natura e pré-tratadas pelos seguintes métodos: organossolve, hidrotérmico, explosão à vapor e ácido diluído. O uso desse material lignocelulósico teve o objetivo de controlar a inibição causada pelos produtos da hidrólise dos lipídios por meio de sua adsorção e, consequentemente, diminuição das concentrações de tais compostos no meio. Outra hipótese era que o bagaço de cana-de-açúcar pudessem agir como co-substrato no processo de biodigestão anaeróbia. Inicialmente realizaram-se ensaios de biodegradabilidade anaeróbia com concentrações crescentes de gordura, que resultaram em relação entre substrato e microrganismo 0,06, 0,1, 0,2, 0,4 e 0,6 g DQO/gSTV. O ensaio com concentração em que foi verificada a inibição severa (0,4 gDQO/gSTV) do processo foi repetido com adição das fibras tratadas e não tratadas. Aos dados de produção acumulada de metano ajustou-se modelo de Gompertz, e parâmetros cinéticos foram inferidos. O bagaço de cana-de-açúcar mostrou potencial como adsorvente de gordura, pois as produções metanogênicas foram superiores à condição inibida sem adição desse material. A adição de fibras pré-tratadas por método organossolve resultou nas maiores produções de metano.

Determination of cyclic and linear siloxanes in wastewater samples by ultrasound-assisted dispersive liquid-liquid microextraction followed by gas chromatography-mass spectrometry

A fast, simple and environmentally friendly ultrasound-assisted dispersive liquid-liquid microextraction (USA-DLLME) procedure has been developed to preconcentrate eight cyclic and linear siloxanes from wastewater samples prior to quantification by gas chromatography-mass spectrometry (GC-MS). A two-stage multivariate optimization approach has been developed employing a Plackett-Burman design for screening and selecting the significant factors involved in the USA-DLLME procedure, which was later optimized by means of a circumscribed central composite design. The optimum conditions were: extractant solvent volume, 13 µL; solvent type, chlorobenzene; sample volume, 13 mL; centrifugation speed, 2300 rpm; centrifugation time, 5 min; and sonication time, 2 min. Under the optimized experimental conditions the method gave levels of repeatability with coefficients of variation between 10 and 24% (n=7). Limits of detection were between 0.002 and 1.4 µg L−1. Calculated calibration curves gave high levels of linearity with correlation coefficient values between 0.991 and 0.9997. Finally, the proposed method was applied for the analysis of wastewater samples. Relative recovery values ranged between 71–116% showing that the matrix had a negligible effect upon extraction. To our knowledge, this is the first time that combines LLME and GC-MS for the analysis of methylsiloxanes in wastewater samples.

Influence of thymol and silver nanoparticles on the degradation of poly(lactic acid) based nanocomposites: thermal and morphological properties

Biopolymers, such as poly(lactic acid) (PLA), have been proposed as environmentally-friendly alternatives in applications such as food packaging. In this work, silver nanoparticles and thymol were used as active additives in PLA matrices, combining the antibacterial activity of silver with the antioxidant performance of thymol. The combined action of both additives influenced PLA thermal degradation in ternary systems. DSC results showed that the addition of thymol resulted in a clear decrease of the glass transition temperature (Tg) of PLA, suggesting its plasticizing effect in PLA matrices. Slight modifications in mechanical properties of dog-bone bars were also observed after the addition of the active components, especially in the elastic modulus. FESEM analyses showed the good distribution of active additives through the PLA matrix, obtaining homogenous surfaces and highlighting the presence of silver nanoparticles successfully embedded into the bulk matrix. Degradation of these PLA-based nanocomposites with thymol and silver nanoparticles in composting conditions indicated that the inherent biodegradable character of this biopolymer was improved after this modification. The obtained nanocomposites showed suitable properties to be used as biodegradable active-food packaging systems with antioxidant and antimicrobial effects.

Characterization of Poly(ε-caprolactone)-Based Nanocomposites Containing Hydroxytyrosol for Active Food Packaging

Antioxidant nano-biocomposites based on poly(ε-caprolactone) (PCL) were prepared by incorporating hydroxytyrosol (HT) and a commercial montmorillonite, Cloisite®30B (C30B), at different concentrations. A full structural, thermal, mechanical and functional characterization of the developed nano-biocomposites was carried out. The presence of the nanoclay and HT increased PCL crystallinity, whereas some decrease in thermal stability was observed. TEM analyses corroborated the good dispersion of C30B into the PCL macromolecular structure as already asserted by XRD tests, since no large aggregates were observed. A reduction in oxygen permeability and increase in elastic modulus were obtained for films containing the nanoclay. Finally, the presence of the nanoclay produced a decrease in the HT release from films due to some interaction between HT and C30B. Results proved that these nano-biocomposites can be an interesting and environmentally-friendly alternative for active food packaging applications with antioxidant performance.

Quantum Dot-Sensitized Solar Cells Based on Directly Adsorbed Zinc Copper Indium Sulfide Colloids

Heavy metal-based quantum dots (QDs) have demonstrated to behave as efficient sensitizers in QD-sensitized solar cells (QDSSCs), as attested by the countless works and encouraging efficiencies reported so far. However, their intrinsic toxicity has arisen as a major issue for the prospects of commercialization. Here, we examine the potential of environmentally friendly zinc copper indium sulfide (ZCIS) QDs for the fabrication of liquid-junction QDSSCs by means of photoelectrochemical measurements. A straightforward approach to directly adsorb ZCIS QDs on TiO2 from a colloidal dispersion is presented. Incident photon-to-current efficiency (IPCE) spectra of sensitized photoanodes show a marked dependence on the adsorption time, with longer times leading to poorer performances. Cyclic voltammograms point to a blockage of the channels of the mesoporous TiO2 film by the agglomeration of QDs as the main reason for the decrease in efficiency. Photoanodes were also submitted to the ZnS treatment. Its effects on electron recombination with the electrolyte are analyzed through electrochemical impedance spectroscopy and photopotential measurements. The corresponding results bring out the role of the ZnS coating as a barrier layer preventing electron leakage toward the electrolyte, as argued in other QD-sensitized systems. The beneficial effect of the ZnS coating is ultimately reflected on the power conversion efficiency of complete devices, reaching values of 2 %. In a more general vein, through these findings, we aim to call the attention to the potentiality of this quaternary alloy, virtually unexplored as a light harvester for sensitized devices.