Assessment of hydrogen sulfide removal from biogas using a field scale anoxic biotrickling filter.

Hydrogen sulphide is one of the most toxic and corrosive compound present in swine-derived biogas streams.In this study, afield scale biotrickling filter for the removal of hydrogen sulfide was investigated.A Biofilter packed with supporting biofilm materials was fed continuously with a proprietary nutrient solution and operatedfor over 73days. The system has been operating with a H2S inlet concentrations ranging from 1,000to 3,000 ppm.Significant removal efficiencies >95% was demonstrated. pH of the stock feeding solution decreased from 6.2 to as low as 3.5within couple days.The resulting drop in pH provided circumstantial evidence to support biological H2 Soxidation to sulphuric acid by sulfide-oxidizers. Sulfur precipitation was also observed to occur. The results suggested that H2S removal from biogas stream can be efficiently achieved using portable, low cost and maintenance free biotrickling filters.

Development of suberin films driven by an ionic liquid-based depolymerisation process

Dissertation presented to obtain the Ph.D degree in Chemistry

Electrodialytic remediation of two types of air pollution control residues and their applicability in construction materials

Dissertação para obtenção do Grau de Mestre em Engenharia do Ambiente Perfil de Engenharia de Sistemas Ambientais

The brushstroke and materials of Amadeo de Souza-Cardoso combined in an authentication tool

Nowadays, authentication studies for paintings require a multidisciplinary approach, based on the contribution of visual features analysis but also on characterizations of materials and techniques. Moreover, it is important that the assessment of the authorship of a painting is supported by technical studies of a selected number of original artworks that cover the entire career of an artist. This dissertation is concerned about the work of modernist painter Amadeo de Souza-Cardoso. It is divided in three parts. In the first part, we propose a tool based on image processing that combines information obtained by brushstroke and materials analysis. The resulting tool provides qualitative and quantitative evaluation of the authorship of the paintings; the quantitative element is particularly relevant, as it could be crucial in solving authorship controversies, such as judicial disputes. The brushstroke analysis was performed by combining two algorithms for feature detection, namely Gabor filter and Scale Invariant Feature Transform. Thanks to this combination (and to the use of the Bag-of-Features model), the proposed method shows an accuracy higher than 90% in distinguishing between images of Amadeo’s paintings and images of artworks by other contemporary artists. For the molecular analysis, we implemented a semi-automatic system that uses hyperspectral imaging and elemental analysis. The system provides as output an image that depicts the mapping of the pigments present, together with the areas made using materials not coherent with Amadeo’s palette, if any. This visual output is a simple and effective way of assessing the results of the system. The tool proposed based on the combination of brushstroke and molecular information was tested in twelve paintings obtaining promising results. The second part of the thesis presents a systematic study of four selected paintings made by Amadeo in 1917. Although untitled, three of these paintings are commonly known as BRUT, Entrada and Coty; they are considered as his most successful and genuine works. The materials and techniques of these artworks have never been studied before. The paintings were studied with a multi-analytical approach using micro-Energy Dispersive X-ray Fluorescence spectroscopy, micro-Infrared and Raman Spectroscopy, micro-Spectrofluorimetry and Scanning Electron Microscopy. The characterization of Amadeo’s materials and techniques used on his last paintings, as well as the investigation of some of the conservation problems that affect these paintings, is essential to enrich the knowledge on this artist. Moreover, the study of the materials in the four paintings reveals commonalities between the paintings BRUT and Entrada. This observation is supported also by the analysis of the elements present in a photograph of a collage (conserved at the Art Library of the Calouste Gulbenkian Foundation), the only remaining evidence of a supposed maquete of these paintings. The final part of the thesis describes the application of the image processing tools developed in the first part of the thesis on a set of case studies; this experience demonstrates the potential of the tool to support painting analysis and authentication studies. The brushstroke analysis was used as additional analysis on the evaluation process of four paintings attributed to Amadeo, and the system based on hyperspectral analysis was applied on the painting dated 1917. The case studies therefore serve as a bridge between the first two parts of the dissertation.

Light harvesting in solar cells using natural pigments from red fruits adsorbed to mesoporous TiO2

Nature has developed strategies to present us with a wide variety of colours, from the green of leaves to the bright colours seen in flowers. Anthocyanins are between these natural pigments that are responsible for the great diversity of colours seen in flowers and fruits. Anthocyanins have been used to sensitize titanium dioxide (TiO2) in Dye-Sensitized Solar Cells (DSSCs). DSSCs have become one of the most popular research topic in photovoltaic cells due to their low production costs when compared to other alternatives. DSSCs are inspired in what happens in nature during photosynthesis. A primary charge separation is achieved by means of a photoexcited dye capable of performing the electron injection into the conduction band of a wide band-gap semiconductor, usually TiO2. With this work we aimed to synthesize a novel mesoporous TiO2 structure as the semiconductor in order to increase the dye loading. We used natural occurring dyes such as anthocyanins and their synthetic flavylium relatives, as an alternative to the widely used metal complexes of Ru(II) which are expensive and are environmentally unsafe. This offers not only the chance to use safer dyes for DSSCs, but also to take profit of waste biological products, such as wine and olive oil production residues that are heavily loaded with anthocyanin dyes. We also performed a photodegradation study using TiO2 as the catalyst to degrade dye contaminants, such as those from the wine production waste, by photo-irradiation of the system in the visible region of the light spectrum. We were able to succeed in the synthesis of mesoporous TiO2 both powder and thin film, with a high capacity to load a large amount of dye. We proved the concept of photodegradation using TiO2 as catalyst. And finally, we show that wine production waste is a possible dye source to DSSCs application.

Spray coating of oxide and chalcogenide semiconductor layers for TFT application

This work documents the deposition and optimization of semiconductor thin films using chemical spray coating technique (CSC) for application on thin-film transistors (TFTs), with a low-cost, simple method. CSC setup was implemented and explored for industrial application, within Holst Centre, an R&D center in the Netherlands. As zinc oxide had already been studied within the organization, it was used as a standard material in the initial experiments, obtaining typical mobility values of 0.14 cm2/(V.s) for unpatterned TFTs. Then, oxide X layer characteristics were compared for films deposited with CSC at 40°C and spin-coating. The mobility of the spin-coated TFTs was 103 cm2/(V.s) higher, presumably due to the lack of uniformity of spray-coated film at such low temperatures. Lastly, tin sulfide, a relatively unexplored material, was deposited by CSC in order to obtain functional TFTs and explore the device’s potential for working as a phototransistor. Despite the low mobilities of the devices, a sensitive photodetector was made, showing drain current variation of nearly one order of magnitude under yellow light. CSC technique’s simplicity and versatility was confirmed, as three different semiconductors were successfully implemented into functional devices.

Assessing the feasibility of impregnating phase change materials in lightweight aggregate for development of thermal energy storage systems

This paper assesses the feasibility of impregnation/encasement of phase change materials (PCMs) in lightweight aggregates (LWAs). An impregnation process was adopted to carry out the encasement study of two different PCMs in four different LWAs. The leakage of the impregnated/encased PCMs was studied when they were submitted to freeze/thawing and oven drying tests, separately. The results confirmed that, the impregnation/encasement method is effective with respect to the large thermal energy storage density, and can be suitable for applications were PCMs cannot be incorporated directly such as asphalt road pavements.

Affordable prefabricated modular houses using cement and polymer based materials and advanced design tools

By taking advantage of the appropriate use of cement and polymer based materials and advanced computational tools, a pre-fabricated affordable house was built in a modular system. Modular system refers to the complete structure that is built-up by assembling pre-fabricated sandwich panels composed of steel fibre reinforced self-compacting concrete (SFRSCC) outer layers that are connected by innovative glass fibre reinforced polymer (GFRP) connectors, resulting in a panel with adequate structural, acoustic, and thermal insulation properties. The modular house was prepared for a typical family of six members, but its living area can be easily increased by assembling other pre-fabricated elements. The speed of construction and the cost of the constructive elements make these houses competitive when compared to traditional solutions. In this paper the relevant research subjacent to this project (LEGOUSE) is briefly described, as well as the construction process of the built real scale prototype.

Mechanical, fatigue and wear properties of sintered Carbon Nanotube-based functionally graded materials

Tese de Doutoramento Engenharia Mecânica

Micro- and mesoporous structures as drug delivery carriers for salicylic acid

The potential of salicylic acid (SA) encapsulated in porous materials as drug delivery carriers for cancer treatment was studied. Different porous structures, the microporous zeolite NaY, and the mesoporous SBA-15 and MCM-41 were used as hosts for the anti-inflammatory drug. Characterization with different techniques (FTIR, UV/vis, TGA, 1H NMR, and 13C CPMAS NMR) demonstrated the successful loading of SA into the porous hosts. The mesoporous structures showed to be very efficient to encapsulate the SA molecule. The obtained drug delivery systems (DDS) accommodated 0.74 mmol (341 mg/gZEO) in NaY and 1.07 mmol (493 mg/gZEO) to 1.23 mmol (566 mg/gZEO) for SBA-15 and MCM-41, respectively. Interactions between SA molecules and pore structures were identified. A fast and unrestricted liberation of SA at 10 min of the dissolution assay was achieved with 29.3, 46.6, and 50.1 µg/mL of SA from NaY, SBA-15, and MCM-41, respectively, in the in vitro drug release studies (PBS buffer pH 7.4, 37 °C). Kinetic modeling was used to determine the release patterns of the DDS. The porous structures and DDS were evaluated on Hs578T and MDA-MB-468 breast cancer cell lines viability. The porous structures are nontoxic to cancer cells. Cell viability reduction was only observed after the release of SA from MCM- 41 followed by SBA-15 in both breast cancer cell lines.

Highly robust chitosan hydrogels via a fast, simple and biocompatible dual crosslinking-based process

Load-bearing soft tissues such as cartilage, blood vessels and muscles are able to withstand a remarkable compressive stress of several MPa without fracturing. Interestingly, most of these structural tissues are mainly composed of water and in this regard, hydrogels, as highly hydrated 3D-crosslinked polymeric networks, constitute a promising class of materials to repair lesions on these tissues. Although several approaches can be employed to shape the mechanical properties of artificial hydrogels to mimic the ones found on biotissues, critical issues regarding, for instance, their biocompatibility and recoverability after loading are often neglected. Therefore, an innovative hydrogel device made only of chitosan (CHI) was developed for the repair of robust biological tissues. These systems were fabricated through a dual-crosslinking process, comprising a photo- and an ionic-crosslinking step. The obtained CHIbased hydrogels exhibited an outstanding compressive strength of ca. 20 MPa at 95% of strain, which is several orders of magnitude higher than those of the individual components and close to the ones found in native soft tissues. Additionally, both crosslinking processes occur rapidly and under physiological conditions, enabling cellsâ encapsulation as confirmed by high cell survival rates (ca. 80%). Furthermore, in contrast with conventional hydrogels, these networks quickly recover upon unloading and are able to keep their mechanical properties under physiological conditions as result of their non-swell nature.

An overview of the brewing process

The first chapter of this book has an introductory character, which discusses the basics of brewing. This includes not only the essential ingredients of beer, but also the steps in the process that transforms the raw materials (grains, hops) into fermented and maturated beer. Special attention is given to the processes involving an organized action of enzymes, which convert the polymeric macromolecules present in malt (such as proteins and polysaccharides) into simple sugars and amino acids; making them available/assimilable for the yeast during fermentation.

Effect of different carbon materials as electron shuttles in the anaerobic biotransformation of nitroanilines

Aromatic amines resulted from azo dyes biotransformation under anaerobic conditions are generally recalcitrant to further anaerobic degradation. The catalytic effect of carbon materials (CM) on the reduction of azo dyes is known and has been confirmed in this work by increasing 3-fold the biological reduction rate of Mordant Yellow 1 (MY1). The resulting m-nitroaniline (m-NoA) was further degraded to m-phenylenediamine (m-Phe) only in the presence of CM. The use of CM to degraded anaerobically aromatic amines resulted from azo dye reduction was never reported before. In the sequence, we studied the effect of different CM on the bioreduction of o-, m- and p-NoA. Three microporous activated carbons with different surface chemistry, original (AC0), chemical oxidized with HNO3 (ACHNO3) and thermal treated (ACH2), and three mesoporous carbons, xerogels (CXA and CXB) and nanotubes (CNT) were assessed. In the absence of CM, NoA were only partially reduced to the corresponding Phe, whereas in the presence of CM, more than 90% was converted to the corresponding Phe. ACH2 and AC0 were the best electron shuttles, increasing the rates up to 8-fold. In 24h, the biological treatment of NoA and MY1 with AC0, decreased up to 88% the toxicity towards a methanogenic consortium, as compared to the non-treated solutions. This article is protected by copyright. All rights reserved

Aproximación al diseño de sistemas de bio-reactores para la delignificación de materiales lignocelulósicos y para la decontaminación de suelos y efluentes. Approximation to the design of bio-reactors systems for the delignificación of lignocellulosic materials and for the decontamination of soil and effluents

Los materiales lignocelulósicos residuales de las actividades agroindustriales pueden ser aprovechados como fuente de lignina, hemicelulosa y celulosa. El tratamiento químico del material lignocelulósico se debe enfrentar al hecho de que dicho material es bastante recalcitrante a tal ataque, fundamentalmente debido a la presencia del polímero lignina. Esto se puede lograr también utilizando hongos de la podredumbre blanca de la madera. Estos producen enzimas lignolíticas extracelulares fundamentalmente Lacasa, que oxida la lignina a CO2. Tambien oxida un amplio rango de sustratos ( fenoles, polifenoles, anilinas, aril-diaminas, fenoles metoxi-sustituídos, y otros), lo cual es una buena razón de su atracción para aplicaciones biotecnológicas. La enzima tiene potencial aplicación en procesos tales como en la delignificación de materiales lignocelulósicos y en el bioblanqueado de pulpas para papel, en el tratamiento de aguas residuales de plantas industriales, en la modificación de fibras y decoloración en industrias textiles y de colorantes, en el mejoramiento de alimentos para animales, en la detoxificación de polutantes y en bioremediación de suelos contaminados. También se la ha utilizado en Q.Orgánica para la oxidación de grupos funcionales, en la formación de enlaces carbono- nitrógeno y en la síntesis de productos naturales complejos. HIPOTESIS: Los hongos de podredumbre blanca, y en condiciones óptimas de cultivo producen distintos tipos de enzimas oxidasas, siendo las lacasas las más adecuadas para explorarlas como catalizadores en los siguientes procesos:  Delignificación de residuos de la industria forestal con el fin de aprovechar tales desechos en la alimentación animal.  Decontaminación/remediación de suelos y/o efluentes industriales. Se realizarán los estudios para el diseño de bio-reactores que permitan responder a las dos cuestiones planteadas en la hipótesis. Para el proceso de delignificación de material lignocelulósico se proponen dos estrategias: 1- tratar el material con el micelio del hongo adecuando la provisión de nutrientes para un desarrollo sostenido y favorecer la liberación de la enzima. 2- Utilizar la enzima lacasa parcialmente purificada acoplada a un sistema mediador para oxidar los compuestos polifenólicos. Para el proceso de decontaminación/remediación de suelos y/o efluentes industriales se trabajará también en dos frentes: 3) por un lado, se ha descripto que existe una correlación positiva entre la actividad de algunas enzimas presentes en el suelo y la fertilidad. En este sentido se conoce que un sistema enzimático, tentativamente identificado como una lacasa de origen microbiano es responsable de la transformación de compuestos orgánicos en el suelo. La enzima protege al suelo de la acumulación de compuestos orgánicos peligrosos catalizando reacciones que involucran degradación, polimerización e incorporación a complejos del ácido húmico. Se utilizarán suelos incorporados con distintos polutantes(por ej. policlorofenoles ó cloroanilinas.) 4) Se trabajará con efluentes industriales contaminantes (alpechínes y/o el efluente líquido del proceso de desamargado de las aceitunas). The lignocellulosic raw materials of the agroindustrial activities can be taken advantage as source of lignin, hemicellulose and cellulose. The chemical treatment of this material is not easy because the above mentioned material is recalcitrant enough to such an assault, due to the presence of the lignin. This can be achieved also using the white-rot fungi of the wood. It produces extracellular ligninolitic enzymes, fundamentally Laccase, which oxidizes the lignin to CO2. The enzyme has application in such processes as in the delignification of lignocellulosic materials and in the biobleaching of fibers for paper industry, in the treatment of waste water of industrial plants, in the discoloration in textile industries, in the improvement of food for ruminants, in the detoxification of polutants and in bioremediation of contaminated soils. HYPOTHESIS: The white-rot fungi produce different types of enzymes, being the laccases the most adapted to explore them as catalysts in the following processes:  Delignification of residues of the forest industry in order to take advantage of such waste in the animal feed.  Decontamination of soils and / or waste waters. The studies will be conducted for the design of bio reactors that allow to answer to both questions raised in the hypothesis. For the delignification process of lignocellulosic material they propose two strategies: 1- to treat the material with the fungi 2-to use the partially purified enzyme to oxidize the polyphenolic compounds. For the soil and/or waste water decontamination process, we have: 3- Is know that the enzyme protects to the soil of the accumulation of organic dangerous compounds catalyzing reactions that involve degradation, polymerization and incorporation to complexes of the humic acid. There will be use soils incorporated into different pollutants. 4- We will work with waste waters (alpechins or the green olive debittering effluents.