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.

A poluição gerada por máquinas de combustão interna movidas à diesel - a questão dos particulados. Estratégias atuais para a redução e controle das emissões e tendências futuras

The exhaust emissions of vehicles greatly contribute to environmental pollution. Diesel engines are extremely fuel-efficient. However, the exhaust compounds emitted by diesel engines are both a health hazard and a nuisance to the public. This paper gives an overview of the emission control of particulates from diesel exhaust compounds. The worldwide emission standards are summarized. Possible devices for reducing diesel pollutants are discussed. It is clear that after-treatment devices are necessary. Catalytic converters that collect particulates from diesel exhaust and promote the catalytic burn-off are examined. Finally, recent trends in diesel particulate emission control by novel catalysts are presented.

Desenvolvimento e aplicação de sistema passivo de coleta de poluentes atmosféricos para monitoramento de Cd, Cr, Pb, Cu, Fe, Mn, Zn e particulados totais

The objective of this study was to assess a new monitoring technique of particulate and trace metals in the atmosphere via the use of a passive sampler of air pollutants in the city of Goiânia. The average particulate weight and average concentrations of metals Fe, Cr, Zn, Pb, Cu, Mn, and Cd were 0.1104 g and 257.5; 23.4; 17.8; 6.7; 1.9; 0.8; 0.2 μg/m²/day, respectively. Higher Pb and Cr concentrations were obtained in areas with intense traffic. This study revealed that it is possible to monitor trace metals with passive sampling, developed at a low cost and operational facility.

Estudo da influência dos particulados no fenômeno de agregação dos asfaltenos por espectrometria de varredura óptica

The processing of national petroleums causes many operational problems due to the asphaltene aggregation phenomena. To evaluate the behavior of these phenomena, a study based on optical scan technique was carried out to understand the behavior of pure oils and their mixtures. The evaluation according to criteria established by ASTM D7061-06¹ gives a result of asphaltene flocculation of according to the separability number. In this study, the aspects related to the existence of colloidal forms of peptized asphaltenes in distinct solvents present in petroleums can cause changes in the kinetics of asphaltene flocculation.

Comparación del efecto protector de la respuesta inmune humoral inducida por antígenos solubles y particulados de Nocardia brasiliensis .html Luz Isabel Pérez Rivera.

Tesis (Doctorado) U.A.N.L.

Avaliação do efeito de particulados sólidos na eficiência de um inibidor de corrosão recomendado para meios salinos com CO2

The main problem on the exploration activity on petroleum industry is the formation water resulted on the fields producing. The aggravating of this problem is correlated with the advancing technologies used on the petroleum extractions and on its secondary approach objecting the reobtainment of this oil. Among the main contaminants of the water formation are corrosives gases such as: O2, CO2 and H2S, some solids in suspension and dissolved salts. Concerning to those gases the CO2 is the one that produce significant damage for carbon steel on corrosion process of the petroleum and gas industries. Corrosion inhibitors for carbon steel in formation water is one of the most used agents in control of those damages. In this context, the poor investigations of carbon steel corrosion proceeding from solids in suspension is an opened field for studies. On this work the inhibitor effect of the commercial CORRTREAT 703 was evaluated on some specific solids in suspension at saline medium containing 10.000 ppm of de-aerated chloride using CO2 until non oxygen atmosphere been present. For that, quartz, calcium carbonate, magnetite and iron sulphide were subjected to this investigation as the selected solids. The effect of this inhibitor on corrosion process correlated with those specific solids, was measured using electrochemical (resistance of linear polarization and galvanic pair) and gravimetrical techniques. During all the experimental work important parameters were monitored such as: pH, dissolved oxygen, temperature, instantaneous corrosion rate and galvanic current. According to the obtained results it was proved that the suspension solids calcium carbonate and iron sulphide decrease the corrosion process in higher pH medium. Meanwhile the quartz and magnetite been hardness increase corrosion by broking of the passive layer for erosion. In the other hand, the tested inhibitor in concentration of 50 ppm, showed to be effective (91%) in this corrosion process

Desgaste corrosivo-cavitativo-erosivo de um aço-carbono em meio aquoso com frações de sal (NaCl), CO2 e particulados sólidos (SiO2)

A batch of eighty-four coupons of low carbon steel were investigated at laboratory conditions under a corrosive, cavitative-corrosive (CO2) and corrosive-erosive (SiO2 + CO2) in an aqueous salt solution and two levels of temperature. The following measurements were made on Vickers (HV0,05, HV0,10, HV0,20) Microhardness tests at three levels of subsurface layer. A turbulent flow collided on the cylindrical sample, with and without mechanical stirring and gas bubbling, with and without fluid contamination by solid particles of SiO2, at two temperatures. Surface Roughness and Waviness, under two conditions "as received, after machining" and "after worn out", as well as gravimetric and electrochemical parameter were measured on the two opposite generatrices of each cylindrical sample, on the flow upstream (0°) and downstream (180°) by Profilometry, Mass Variation and Linear Polarization Resistance (LPR). The results of the Microhardness and Surface Texture of all coupons were subjected to statistical comparison, using the software Statgraphics® Centurion XVI, 95% statistical certainty, and significant differences were observed in some arrays of measurements. The corrosive wear rate measured by LPR and mass variation shown to be sensitive to the presence of bubbles and hydrodynamic fluctuations inside the cell, considering the temperature and contamination of corrosive fluid by solid particles. The main results of visual inspection relative to some topologies of the surface damages involving different mechanisms that were seen to give explanation for some fluctuations in wear rates of the steel experimentally investigated

Propriedades físico-mecânicas de painéis particulados de Eucalyptus saligna e casca de noz macadâmia

Pós-graduação em Engenharia Mecânica - FEG

Projeto, construção de equipamento para obtenção de compósitos de matriz metálica particulados, utilizando o processo de fundição com agitação mecânica

Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)

Estudo da emissão e do controle dos gases e particulados provenientes da queima de biomassa

Pós-graduação em Engenharia Mecânica - FEG

Determinação de Cd, Pb e Cu em particulados atmosféricos da região de Presidente Prudente por análise voltamétrica utilizando eletrodo de mercúrio

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)

Amostragem de poluentes gasosos e particulados emitidos pela queima de biomassa vegetal

The use of biomass as an energy source has been increasing in Brazil, with emphasis on the use of wood biomass, such as bark, wood chips and sawdust, that after receiving the appropriate treatment can be used in burners for power generation. However, from this burning are emitted fine particles known as particulate matter and a wide range of toxic organic and inorganic components in the form of gases that contribute greatly to air pollution and global warming, affecting human health, the environment and climate. The objective of this project was the quantification of gaseous and particulate, using and evaluating the equipment DR4000 ( Dataram 4 ) sampling of particulates smaller than 2.5μm and EUROTRON ( Ecoline 4000 ) when sampling gaseous pollutants, emitted from the burning of biomass in real time in the firing burner to a chimney attached biomass . We note that there are no specific rules that establish emission limits for particulate matter with diameter less than 2.5μm that are most harmful to human health and the highest concentrations reached about 800000μg/m3, for smaller diameters. It is noticeable the need for sampling of pollutants especially in industries that use biomass to fuel that could be implanted emission control equipment

Amostragem de poluentes particulados emitidos pela queima de biomassa em correntes confinadas

It is clear today the ever-accelerating search for new fuels that will eventually replace those that will survive in our society, which are fossil fuels. For this reason, a fuel used since the dawn of humanity and much studied since then, considered the generator of clean, renewable energy, can earn more and more space in the power generation sector, which is biomass. We performed two experiments with two different types of biomass, one from the Amazon rainforest and other pine and eucalyptus as waste from the sawmill UNESP Itapeva. In the first experiment, conducted at the Laboratory of Combustion and Propulsion INPE Cachoeira Paulista were conducted three tests in a chimney with a fan creating forced ventilation, where the biomass was burned and deposited on a support beneath the hood. In the second experiment was conducted to analyze the emission of particulate matter using biomass (waste) from the sawmill on the campus of UNESP experimental Itapeva the burning of it in a burner for heating water for a wood oven. In these experiments we used a particle called DATARAM4 sampler that is capable of sampling both outdoors and inside of pipelines, which is the focus of this work. With this equipment it was possible to measure the concentration of particulate matter in all the firings as above, and compare them to levels acceptable in the current law, always trying to analyze the so-called fine particles, which are those with diameters less than 2.5 μm. Using data obtained from the equipment was also possible to evaluate the diametral distribution of particulate matter in question, and verify which phases of the flares in the concentration and the diameters of the particles are the most critical. In this work we concluded that in all firings conducted concentrations of particulate matter were higher than that allowed by the law, and the diameters were found that are more harmful to human health

Onde devemos analisar o reparo ósseo após a colocação de enxertos particulados em cavidades ósseas cirúrgicas

Na avaliação das propriedades de biomateriais particulados enxertados em cavidades ósseas cirúrgicas, deve-se considerar separadamente dois ambientes diferentes. Em primeiro lugar, o que ocorre diretamente na interface das partículas com o coágulo sanguíneo e o tecido de granulação, inclusive a osteogênese? Em segundo, o que ocorre nos espaços entre as partículas, distante de sua superfície: quais as reações teciduais induzidas, inclusive a osteogênese? Nesses espaços, como evoluem o coágulo sanguíneo, o tecido de granulação e a neoformação óssea? A mais preponderante das reações frente aos biomateriais particulados deve estar relacionada com o que ocorre diretamente sobre a superfície das partículas e se, ao longo do tempo, essas partículas serão ou não reabsorvidas para dar lugar ao tecido ósseo e restabelecer por completo a normalidade no local.