Development of bioplastics from agro-wastes

Poster

Desarrollo de sistemas nano/micro-particulados con aplicación en la fotodegradación selectiva de contaminantes orgánicos en solución. Development of nano / micro-particles systems with application to selective photodegradation of organic pollutants in solution.

IDENTIFICACIÓN DEL PROBLEMA DE ESTUDIO. Las sustancias orgánicas solubles en agua no biodegradables tales como ciertos herbicidas, colorantes industriales y metabolitos de fármacos de uso masivo son una de las principales fuentes de contaminación en aguas subterráneas de zonas agrícolas y en efluentes industriales y domésticos. Las reacciones fotocatalizadas por irradiación UV-visible y sensitizadores orgánicos e inorgánicos son uno de los métodos más económicos y convenientes para la descomposición de contaminantes en subproductos inocuos y/o biodegradables. En muchas aplicaciones es deseable un alto grado de especificidad, efectividad y velocidad de degradación de un dado agente contaminante que se encuentra presente en una mezcla compleja de sustancias orgánicas en solución. En particular son altamente deseables sistemas nano/micro -particulados que formen suspensiones acuosas estables debido a que estas permiten una fácil aplicación y una eficaz acción descontaminante en grandes volúmenes de fluidos. HIPÓTESIS Y PLANTEO DE LOS OBJETIVOS. El objetivo general de este proyecto es desarrollar sistemas nano/micro particulados formados por polímeros de impresión molecular (PIMs) y foto-sensibilizadores (FS). Un PIMs es un polímero especialmente sintetizado para que sea capaz de reconocer específicamente un analito (molécula plantilla) determinado. La actividad de unión específica de los PIMs en conjunto con la capacidad fotocatalizadora de los sensibilizadores pueden ser usadas para lograr la fotodescomposición específica de moléculas “plantilla” (en este caso un dado contaminante) en soluciones conteniendo mezclas complejas de sustancias orgánicas. MATERIALES Y MÉTODOS A UTILIZAR. Se utilizaran técnicas de polimerización en mini-emulsión para sintetizar los sistemas nano/micro PIM-FS para buscar la degradación de ciertos compuestos de interés. Para caracterizar eficiencias, mecanismos y especificidad de foto-degradación en dichos sistemas se utilizan diversas técnicas espectroscópicas (estacionarias y resueltas en el tiempo) y de cromatografía (HPLC y GC). Así mismo, para medir directamente distribuciones de afinidades de unión y eficiencia de foto-degradación se utilizaran técnicas de fluorescencia de molécula/partícula individual. Estas determinaciones permitirán obtener resultados importantes al momento de analizar los factores que afectan la eficiencia de foto-degradación (nano/micro escala), tales como cantidad y ubicación de foto- sensibilizadores en las matrices poliméricas y eficiencia de unión de la plantilla y los productos de degradación al PIM. RESULTADOS ESPERADOS. Los estudios propuestos apuntan a un mejor entendimiento de procesos foto-iniciados en entornos nano/micro-particulados para aplicar dichos conocimientos al diseño de sistemas optimizados para la foto-destrucción selectiva de contaminantes acuosos de relevancia social; tales como herbicidas, residuos industriales, metabolitos de fármacos de uso masivo, etc. IMPORTANCIA DEL PROYECTO. Los sistemas nano/micro-particulados PIM-FS que se propone desarrollar en este proyecto se presentan como candidatos ideales para tratamientos específicos de efluentes industriales y domésticos en los cuales se desea lograr la degradación selectiva de compuestos orgánicos. Los conocimientos adquiridos serán indispensables para construir una plataforma versátil de sistemas foto-catalíticos específicos para la degradación de diversos contaminantes orgánicos de interés social. En lo referente a la formación de recursos humanos, el proyecto propuesto contribuirá en forma directa a la formación de 3 estudiantes de postgrado y 2 estudiantes de grado. En las capacidades institucionales se contribuirá al acondicionamiento del Laboratorio para Microscopía Óptica Avanzada (LMOA) en el Dpto. de Química de la UNRC y al montaje de un sistema de microscopio de fluorescencia que permitirá la aplicación de técnicas avanzadas de espectroscopia de fluorescencia de molecula individual. Water-soluble organic molecules such as certain non-biodegradable herbicides, industrial dyes and metabolites of widespread use drugs are a major source of pollution in groundwater from agricultural areas and in industrial and domestic effluents. Photo-catalytic reactions by UV-visible irradiation and organic sensitizers are one of the most economical and convenient methods for the decomposition of pollutants into harmless byproducts. In many applications it is highly desirable a high degree of specificity, effectiveness and speed of degradation of specific pollutants present in a complex mixture. In particular nano/micro-particles systems that form stable aqueous suspensions are highly desirable because they allow for easy application and effective decontamination of large volumes of fluids. Herein we propose the development of nano/micro particles composed by molecularly imprinted polymers (MIP) and photo-sensitizers (PS). The specific binding of MIP and the photo-catalytic ability of the sensitizers are used to achieve the photo-decomposition of specific "template" molecules in complex mixtures. Mini-emulsion polymerization techniques will be used to synthesize nano/micro MIP-FS systems. Spectroscopy (steady-state and time resolved) and chromatography (GC and HPLC) will be used to characterize efficiency, mechanisms and specificity of photo-degradation in these systems. In addition single molecule/particle fluorescence spectroscopy techniques will be used to directly measure distributions of binding affinities and photo-degradation efficiency in individual particles. The proposed studies point to a more detailed understanding of the factors affecting the photo-degradation efficiency in nano/micro-particles and to apply that knowledge in the design of optimized systems for photo-selective destruction of socially relevant aqueous pollutants.

Development of a new method for the characterisation of bioreactors concerning heat and mass transfer

Since the specific heat transfer coefficient (UA) and the volumetric mass transfer coefficient (kLa) play an important role for the design of biotechnological processes, different techniques were developed in the past for the determination of these parameters. However, these approaches often use imprecise dynamic methods for the description of stationary processes and are limited towards scale and geometry of the bioreactor. Therefore, the aim of this thesis was to develop a new method, which overcomes these restrictions. This new approach is based on a permanent production of heat and oxygen by the constant decomposition of hydrogen peroxide in continuous mode. Since the degradation of H2O2 at standard conditions only takes place by the support of a catalyst, different candidates were investigated for their potential (regarding safety issues and reaction kinetic). Manganese-(IV)-oxide was found to be suitable. To compensate the inactivation of MnO2, a continuous process with repeated feeds of fresh MnO2 was established. Subsequently, a scale-up was successfully carried out from 100 mL to a 5 litre glass bioreactor (UniVessel®)To show the applicability of this new method for the characterisation of bioreactors, it was compared with common approaches. With the newly established technique as well as with a conventional procedure, which is based on an electrical heat source, specific heat transfer coefficients were measured in the range of 17.1 – 24.8 W/K for power inputs of about 50 – 70 W/L. However, a first proof of concept regarding the mass transfer showed no constant kLa for different dilution rates up to 0.04 h-1.Based on this, consecutive studies concerning the mass transfer should be made with higher volume flows, due to more even inflow rates. In addition, further experiments are advisable, to analyse the heat transfer in single-use bioreactors and in larger common systems.

The building blocks of international ecological footprint inequality: a regression-based decomposition

This paper performs an empirical Decomposition of International Inequality in Ecological Footprint in order to quantify to what extent explanatory variables such as a country’s affluence, economic structure, demographic characteristics, climate and technology contributed to international differences in terms of natural resource consumption during the period 1993-2007. We use a Regression-Based Inequality Decomposition approach. As a result, the methodology extends qualitatively the results obtained in standard environmental impact regressions as it comprehends further social dimensions of the Sustainable Development concept, i.e. equity within generations. The results obtained point to prioritizing policies that take into account both future and present generations.

The Building Blocks of International Ecological Footprint inequality: A Regression-Base Decomposition

This paper performs an empirical Decomposition of International Inequality in Ecological Footprint in order to quantify to what extent explanatory variables such as a country’s affluence, economic structure, demographic characteristics, climate and technology contributed to international differences in terms of natural resource consumption during the period 1993-2007. We use a Regression- Based Inequality Decomposition approach. As a result, the methodology extends qualitatively the results obtained in standard environmental impact regressions as it comprehends further social dimensions of the Sustainable Development concept, i.e. equity within generations. The results obtained point to prioritizing policies that take into account both future and present generations. Keywords: Ecological Footprint Inequality, Regression-Based Inequality Decomposition, Intragenerational equity, Sustainable development.

Allowing for heterogeneity in the decomposition of measures of inequality in health

This paper shows how recently developed regression-based methods for the decomposition ofhealth inequality can be extended to incorporate heterogeneity in the responses of health to the explanatory variables. We illustrate our method with an application to the GHQ measure of psychological well-being taken from the British Household Panel Survey. The results suggest that there is an important degree of heterogeneity in the association of health to explanatory variables across birth cohorts and genders which, in turn, accounts for a substantial percentage of the inequality in observed health.

Rate of development of forensically-important Dipterain southern Brazil

Dipteran larvae were collected from rabbit (Oryctolagus cunniculus L.) carcasses during the four seasons in 2005 in the southernmost state of Rio Grande do Sul, Brazil. The larvae were fed ground beef at ambient temperatures following collection from carcasses. The development of each species under these conditions was estimated. The most abundant species in the carcasses were Lucilia eximia (Wiedemann) and Chrysomya albiceps (Wiedemann) (Calliphoridae), and they were found in all seasons. The data were fitted to a linear model that describes the relationship between temperature and linear developmental rating. These two species are primary forensic indicators in southern Brazil. Other species such as Hemilucilia semidiaphana (Rondani) (Calliphoridae), Synthesiomyia nudiseta (Wulp), Muscina stabulans (Fallen) (Muscidae), and Fannia pusio (Wiedemann) (Fanniidae) were forensically less important because they only occurred in high frequency in certain seasons and during the first days of carcass decomposition.

The importance of individual heterogeneity in the decomposition of measures of socioeconomic inequality in health: An approach based on quantile regression

This paper shows how recently developed regression-based methods for thedecomposition of health inequality can be extended to incorporateindividual heterogeneity in the responses of health to the explanatoryvariables. We illustrate our method with an application to the CanadianNPHS of 1994. Our strategy for the estimation of heterogeneous responsesis based on the quantile regression model. The results suggest that thereis an important degree of heterogeneity in the association of health toexplanatory variables which, in turn, accounts for a substantial percentageof inequality in observed health. A particularly interesting finding isthat the marginal response of health to income is zero for healthyindividuals but positive and significant for unhealthy individuals. Theheterogeneity in the income response reduces both overall health inequalityand income related health inequality.

Pedochronology and development of peat bog in the environmental protection area pau-de-fruta - Diamantina, Brazil

In the region of the Serra do Espinhaço Meridional, peat bog is formed in hydromorphic environments developed in sunken areas on the plain surfaces with vegetation adapted to hydromorphic conditions, favoring the accumulation and preservation of organic matter. This pedoenvironment is developed on the regionally predominant quartzite rocks. Peat bog in the Environmental Protection Area - APA Pau-de-Fruta, located in the watershed of Córrego das Pedras, Diamantina,Brazil, was mapped and three representative profiles were morphologically characterized and sampled for physical, chemical and microbiological analyses. The organic matter was fractionated into fulvic acid (FA), humic acids (HA) and humin (H). Two profiles were sampled to determine the radiocarbon age and δ13C. The structural organization of the three profiles is homogeneous. The first two layers consist of fibric, the two subsequent of hemic and the four deepest of sapric peat, showing that organic matter decomposition advances with depth and that the influence of mineral materials in deeper layers is greater. Physical properties were homogeneous in the profiles, but varied in the sampled layers. Chemical properties were similar in the layers, but the Ca content, sum of bases and base saturation differed between profiles. Contents of H predominated in the more soluble organic matter fractions and were accumulated at a higher rate in the surface and deeper layers, while HA levels were higher in the intermediate and FA in the deeper layers. Microbial activity did not vary among profiles and was highest in the surface layers, decreasing with depth. From the results of radiocarbon dating and isotope analysis, it was inferred that bog formation began about 20 thousand years ago and that the vegetation of the area had not changed significantly since then.

Environmental Structural Decomposition Analysis of Italian Emissions, 1995-2005

[spa] El estudio analiza la evolución de los gases de efecto invernadero (GEI) y las emisiones de acidificación para Italia durante el periodo 1995-2005. Los datos muestran que mientras las emisiones que contribuyen a la acidificación han disminuido constantemente, las emisiones de GEI han aumentado debido al aumento de dióxido de carbono. El objetivo de este estudio es poner de relieve cómo diferentes factores económicos, en particular el crecimiento económico, el desarrollo de una tecnología menos contaminante y la estructura del consumo, han impulsado la evolución de las emisiones. La metodología propuesta es un análisis de descomposición estructural (ADE), método que permite descomponer los cambios de la variable de interés entre las diferentes fuerzas y revelar la importancia de cada factor. Por otra parte, este estudio considera la importancia del comercio internacional e intenta incluir el “problema de la responsabilidad”. Es decir, a través de las relaciones comerciales internacionales, un país podría estar exportando procesos de producción contaminantes sin una reducción real de la contaminación implícita en su patrón de consumo. Con este fin, siguiendo primero un enfoque basado en la “responsabilidad del productor”, el ADE se aplica a las emisiones causadas por la producción nacional. Sucesivamente, el análisis se mueve hacia un enfoque basado en la “responsabilidad del consumidor" y la descomposición se aplica a las emisiones relacionadas con la producción nacional o la producción extranjera que satisface la demanda interna. De esta manera, el ejercicio permite una primera comprobación de la importancia del comercio internacional y pone de relieve algunos resultados a nivel global y a nivel sectorial.

Environmental Structural Decomposition Analysis of Italian Emissions, 1995-2005

[spa] El estudio analiza la evolución de los gases de efecto invernadero (GEI) y las emisiones de acidificación para Italia durante el periodo 1995-2005. Los datos muestran que mientras las emisiones que contribuyen a la acidificación han disminuido constantemente, las emisiones de GEI han aumentado debido al aumento de dióxido de carbono. El objetivo de este estudio es poner de relieve cómo diferentes factores económicos, en particular el crecimiento económico, el desarrollo de una tecnología menos contaminante y la estructura del consumo, han impulsado la evolución de las emisiones. La metodología propuesta es un análisis de descomposición estructural (ADE), método que permite descomponer los cambios de la variable de interés entre las diferentes fuerzas y revelar la importancia de cada factor. Por otra parte, este estudio considera la importancia del comercio internacional e intenta incluir el “problema de la responsabilidad”. Es decir, a través de las relaciones comerciales internacionales, un país podría estar exportando procesos de producción contaminantes sin una reducción real de la contaminación implícita en su patrón de consumo. Con este fin, siguiendo primero un enfoque basado en la “responsabilidad del productor”, el ADE se aplica a las emisiones causadas por la producción nacional. Sucesivamente, el análisis se mueve hacia un enfoque basado en la “responsabilidad del consumidor" y la descomposición se aplica a las emisiones relacionadas con la producción nacional o la producción extranjera que satisface la demanda interna. De esta manera, el ejercicio permite una primera comprobación de la importancia del comercio internacional y pone de relieve algunos resultados a nivel global y a nivel sectorial.

Formal development and quantitative verification of dependable systems

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Development of an environmentally friendly method of starch oxidation by hydrogen peroxide and a complex water-soluble Iron catalyst

Oxidized starch is a key component in the paper industry, where it is used as both surfacing sizer and filler. Large quantities are annually used for this purpose; however, the methods for the oxidation are not environmentally friendly. In our research, we have studied the possibility to replace the harmful oxidation agents, such as hypochlorite or iodates and transition metal catalysts, with a more environmentally friendly oxidant, hydrogen peroxide (H2O2), and a special metal complex catalyst (FePcS), of which only a small amount is needed. The work comprised batch and semi-batch studies by H2O2, ultrasound studies of starch particles, determination of low-molecular by-products and determination of the decomposition kinetics of H2O2 in the presence of starch and the catalyst. This resulted in a waste-free oxidation method, which only produces water and oxygen as side products. The starch oxidation was studied in both semi-batch and batch modes in respective to the oxidant (H2O2) addition. The semi-batch mode proved to yield a sufficient degree of substitution (COOH groups) for industrial purposes. Treatment of starch granules by ultrasound was found to improve the reactivity of starch. The kinetic results were found out to have a rather complex pattern – several oxidation phases were observed, apparently due to the fact that the oxidation reaction in the beginning only took place on the surface, whereas after a prolonged reaction time, partial degradation of the solid starch granules allowed further reaction in the interior parts. Batch-mode experiments enabled a more detailed study of the mechanisms of starch in the presence of H2O2 and the catalyst, but yielded less oxidized starch due to rapid decomposition of H2O2 due to its high concentrations. The effect of the solid-liquid (S/L) ratio in the reaction system was studied in batch experiments. These studies revealed that the presence of the catalyst and the starch enhance the H2O2 decomposition.

Formal development of resilient distributed systems

Resilience is the property of a system to remain trustworthy despite changes. Changes of a different nature, whether due to failures of system components or varying operational conditions, significantly increase the complexity of system development. Therefore, advanced development technologies are required to build robust and flexible system architectures capable of adapting to such changes. Moreover, powerful quantitative techniques are needed to assess the impact of these changes on various system characteristics. Architectural flexibility is achieved by embedding into the system design the mechanisms for identifying changes and reacting on them. Hence a resilient system should have both advanced monitoring and error detection capabilities to recognise changes as well as sophisticated reconfiguration mechanisms to adapt to them. The aim of such reconfiguration is to ensure that the system stays operational, i.e., remains capable of achieving its goals. Design, verification and assessment of the system reconfiguration mechanisms is a challenging and error prone engineering task. In this thesis, we propose and validate a formal framework for development and assessment of resilient systems. Such a framework provides us with the means to specify and verify complex component interactions, model their cooperative behaviour in achieving system goals, and analyse the chosen reconfiguration strategies. Due to the variety of properties to be analysed, such a framework should have an integrated nature. To ensure the system functional correctness, it should rely on formal modelling and verification, while, to assess the impact of changes on such properties as performance and reliability, it should be combined with quantitative analysis. To ensure scalability of the proposed framework, we choose Event-B as the basis for reasoning about functional correctness. Event-B is a statebased formal approach that promotes the correct-by-construction development paradigm and formal verification by theorem proving. Event-B has a mature industrial-strength tool support { the Rodin platform. Proof-based verification as well as the reliance on abstraction and decomposition adopted in Event-B provides the designers with a powerful support for the development of complex systems. Moreover, the top-down system development by refinement allows the developers to explicitly express and verify critical system-level properties. Besides ensuring functional correctness, to achieve resilience we also need to analyse a number of non-functional characteristics, such as reliability and performance. Therefore, in this thesis we also demonstrate how formal development in Event-B can be combined with quantitative analysis. Namely, we experiment with integration of such techniques as probabilistic model checking in PRISM and discrete-event simulation in SimPy with formal development in Event-B. Such an integration allows us to assess how changes and di erent recon guration strategies a ect the overall system resilience. The approach proposed in this thesis is validated by a number of case studies from such areas as robotics, space, healthcare and cloud domain.

Studies on oxamyl : analytical method development and investigation of fate in peach seedlings and corn seeds

A high performance liquid chromatographic method employing two columns connected in series and separated~y·a.switching valve has been developed for the analysis of the insecticide/ nematicide oxamyl (methyl-N' ,N'-dimethyl-N-[(methylcarbamoyl) oxy]-l-thiooxarnimidate) and two of its metabolites. A variation of this method involving two reverse phase columns was employed to monitor the persistence and translocation of oxamyl in treated peach seedlings. It was possible to simultaneously analyse for oxamyl and its corresponding oxime (methyl-N',N'-dimethyl-N-hydroxy-l-thiooxamimidate}, a major metabolite of oxamyl in plants, without prior cleanup of the samples. The method allowed detection of 0.058 pg oxamyl and 0.035 p.g oxime. On treated peach leaves oxamyl was found to dissipate rapidly during the first two-week period, followed by a period of slow decomposition. Movement of oxamyl or its oxime did not occur in detectable quantities to untreated leaves or to the root or soil. A second variation of the method which employed a size exclusion column as·the first column and a reverse phase column as the second was used to monitor the degradation of oxamyl in treated, planted corn seeds and was suitable for simultaneous analysis of oxamyl, its oxime and dimethylcyanoformamide (DMCF), a metabolite of oxamyl. The method allowed detection of 0.02 pg oxamyl, 0.02 p.g oxime and 0.005 pg DMCF. Oxamyl was found to persist for a period of 5 - 6 weeks, which is long enough to permit oxamyl seedtreatment to be considered as a potential means of protecting young corn plants from nematode attack. Decomposition was found to be more rapid in unsterilized soil than in sterililized soil. DMCF was found to have a nematostatic effect at high concentrations ( 2,OOOpprn), but at lower concentrations no effect on nematode mobility was observed. Oxamyl, on the other hand, was found to reduce the mobility of nematodes at concentrations down to 4 ppm.