New end-use application for GFRP recyclates as reinforcement for concrete-polymer materials’

Glass fibre-reinforced plastics (GFRP), nowadays commonly used in the construction, transportation and automobile sectors, have been considered inherently difficult to recycle due to both: cross-linked nature of thermoset resins, which cannot be remolded, and complex composition of the composite itself, which includes glass fibres, matrix and different types of inorganic fillers. Presently, most of the GFRP waste is landfilled leading to negative environmental impacts and supplementary added costs. With an increasing awareness of environmental matters and the subsequent desire to save resources, recycling would convert an expensive waste disposal into a profitable reusable material. There are several methods to recycle GFR thermostable materials: (a) incineration, with partial energy recovery due to the heat generated during organic part combustion; (b) thermal and/or chemical recycling, such as solvolysis, pyrolisis and similar thermal decomposition processes, with glass fibre recovering; and (c) mechanical recycling or size reduction, in which the material is subjected to a milling process in order to obtain a specific grain size that makes the material suitable as reinforcement in new formulations. This last method has important advantages over the previous ones: there is no atmospheric pollution by gas emission, a much simpler equipment is required as compared with ovens necessary for thermal recycling processes, and does not require the use of chemical solvents with subsequent environmental impacts. In this study the effect of incorporation of recycled GFRP waste materials, obtained by means of milling processes, on mechanical behavior of polyester polymer mortars was assessed. For this purpose, different contents of recycled GFRP waste materials, with distinct size gradings, were incorporated into polyester polymer mortars as sand aggregates and filler replacements. The effect of GFRP waste treatment with silane coupling agent was also assessed. Design of experiments and data treatment were accomplish by means of factorial design and analysis of variance ANOVA. The use of factorial experiment design, instead of the one-factor-at-a-time method is efficient at allowing the evaluation of the effects and possible interactions of the different material factors involved. Experimental results were promising toward the recyclability of GFRP waste materials as aggregates and filler replacements for polymer mortar, with significant gain of mechanical properties with regard to non-modified polymer mortars.

Impact of prescribed fire on the chemical properties of soil

Prescribed fire is a common forest management tool used in Portugal to reduce the fuel load availability and minimize the occurrence of wildfires. In addition, the use of this technique also causes an impact to ecosystems. In this presentation we propose to illustrate some results of our project in two forest sites, both located in Northwest Portugal, where the effect of prescribed fire on soil properties were recorded during a period of 6 months. Changes in soil moisture, organic matter, soil pH and iron, were examined by Principal Component Analysis multivariate statistics technique in order to determine impact of prescribed fire on these soil properties in these two different types of soils and determine the period of time that these forest soils need to recover to their pre-fire conditions, if they can indeed recover. Although the time allocated to this study does not allow for a widespread conclusion, the data analysis clearly indicates that the pH values are positively correlated with iron values at both sites. In addition, geomorphologic differences between both sampling sites, Gramelas and Anjos, are relevant as the soils’ properties considered have shown different performances in time. The use of prescribed fire produced a lower impact in soils originated from more amended bedrock and therefore with a ticker humus covering (Gramelas) than in more rocky soils with less litter covering (Anjos) after six months after the prescribed fire occurrence.

Conditional probability applied to the definition of limestone geochemical facies: A new Methodological Approach

A new method, based on linear correlation and phase diagrams was successfully developed for processes like the sedimentary process, where the deposition phase can have different time duration - represented by repeated values in a series - and where the erosion can play an important rule deleting values of a series. The sampling process itself can be the cause of repeated values - large strata twice sampled - or deleted values: tiny strata fitted between two consecutive samples. What we developed was a mathematical procedure which, based upon the depth chemical composition evolution, allows the establishment of frontiers as well as the periodicity of different sedimentary environments. The basic tool isn't more than a linear correlation analysis which allow us to detect the existence of eventual evolution rules, connected with cyclical phenomena within time series (considering the space assimilated to time), with the final objective of prevision. A very interesting discovery was the phenomenon of repeated sliding windows that represent quasi-cycles of a series of quasi-periods. An accurate forecast can be obtained if we are inside a quasi-cycle (it is possible to predict the other elements of the cycle with the probability related with the number of repeated and deleted points). We deal with an innovator methodology, reason why it's efficiency is being tested in some case studies, with remarkable results that shows it's efficacy. Keywords: sedimentary environments, sequence stratigraphy, data analysis, time-series, conditional probability.

Soil attributes dynamics evaluation after prescribed burning practice in northwestern Portugal forest

The Portuguese northern forests are often and severely affected by wildfires during the summer season. These occurrences affect significant and rudely all ecosystems, namely soil, fauna and flora. Preventive actions such as prescribed burnings and clear-cut logging are frequently used and have showed a significant reduction of the natural wildfires occurrences. In Portugal, and due to some technical and operational conditions, prescribed burnings in forests are the most common preventive action used to reduce the existing fuel hazard. The overall impacts of this preventive action on Portuguese ecosystems are complex and not fully understood. This work reports to the study of a prescribed burning impact in soil chemical properties, namely pH, humidity and organic matter, by monitoring the soil self-recovery capacity. The experiments were carried out in soil cover over a natural site of Andaluzitic schist, in Gramelas, Caminha, Portugal, who was able to maintain itself intact from prescribed burnings from four years. The composed soil samples were collected from five plots at three different layers (0-3cm, 3-6cm and 6-18cm) 1 day before prescribed fire and after the prescribed fire. The results have shown that the dynamic equilibrium in soil was affected significantly.

Sustainability Evaluation of Biodiesel Produced from Microalgae Chlamydomonas sp Grown in Brewery Wastewater

This study performs a sustainability evaluation of biodiesel from microalga Chlamydomonas sp. grown in 20 % (v/v) of brewery’s wastewater, blended with pentose sugars (xylose, arabinose or ribose resulting from the hydrolysis of brewer’s spent grains (BSG). The life cycle steps considered for the study are: microalgae cultivation, biomass processing and lipids extraction at the brewery site, and its conversion to biodiesel at a dedicated external biofuel’s plant. Three sustainability indicators (LCEE, FER and GW) were considered and calculated using experimental data. Literature data was used, whenever necessary, to complement life cycle data, thus allowing a more accurate sustainability evaluation. A comparative analysis of the biodiesel life cycle steps was also conducted, with the main goal of identifying which steps need to be improved. Results show that biomass processing, especially cell harvesting, microalgae cultivation, and lipids extraction are the main process bottlenecks. It is also analysed the influence on the microalgae biodiesel sustainability of adding each pentose sugar to the cultivation media, concluding that it strongly influences the biomass and lipid productivity. In particular, the addition of xylose is preferable in terms of lipid productivity, but from a sustainability point of view, ribose is the best, though the difference from xylose is not significant. Nevertheless, culture without pentose addition presents the best sustainability results.

Simulação da Central de Cogeração da Refinaria de Matosinhos (Petrogal)

Mestrado em Engenharia Química – Ramo Optimização Energética na Indústria Química

Possibilidade e rentabilidade da utilização do gás de xisto em Portugal

Mestrado em Engenharia Mecânica- Energia

Recovery of acid and base from brackish water by bipolar membrane electrodialysis

Nesta dissertação pretendeu-se estudar a viabilidade do uso de eletrodiálise com membranas bipolares (BM) na recuperação de ácido clorídrico e de hidróxido de sódio a partir de um efluente industrial que contém 1.4 mol/L de cloreto de sódio. Estas membranas mostraram ser uma ferramenta eficiente para a produção de ácidos e bases a partir do respetivo sal. Foi feita uma seleção de diferentes membranas bipolares (Neosepta, Fumatech e PCA) e aniónicas (PC-SA e PC-ACID 60) na tentativa de encontrar a combinação mais adequada para o tratamento do efluente. Dependendo do critério, o melhor arranjo de membranas é o uso de PC-ACID 60 (membrana aniónica), PC-SK (membrana catiónica) e membranas bipolares do tipo Neosepta para maior pureza dos produtos; membranas bipolares Fumatech para maior eficiência de dessalinização e membranas bipolares PCA para um maior grau de dessalinização. Tecnologicamente foi possível obter uma dessalinização de 99.8% em quatro horas de funcionamento em modo batch com recirculação de todas as correntes. Independentemente da combinação usada é recomendável que o processo seja parado quando a densidade de corrente deixa de ser máxima, 781 A/m2. Assim é possível evitar o aumento de impurezas nos produtos, contra difusão, descida instantânea do pH e uma dessalinização pouco eficiente. A nível piloto o principal fornecedor de membranas e unidade de tratamento “stack” é a marca alemã PCA. Sendo assim realizaram-se ensaios de repetibilidade, contra difusão, avaliação económica e upscaling utilizando as membranas bipolares PCA. A nível económico estudou-se o uso de dois tipos de unidades de tratamento; EDQ 380 e EDQ 1600, para diferentes níveis de dessalinização (50, 75 e 80%). Tendo em conta a otimização económica, é recomendável uma dessalinização máxima de 80%, uma vez que a eficiência de processo a este ponto é de 40%. A aplicação do método com a unidade EDQ 1600 para uma dessalinização de 50% é a mais vantajosa economicamente, com custos de 16 €/m3 de efluente tratado ou 0,78 €/kg Cl- removido. O número de unidades necessárias é 4 posicionados em série.

Electrospun Polyaniline-Reduced Graphene Oxide Composite Nanofibers Based High Sensitive Ammonia Gas Sensor

Ammonia is an important gas in many power plants and industrial processes so its detection is of extreme importance in environmental monitoring and process control due to its high toxicity. Ammonia’s threshold limit is 25 ppm and the exposure time limit is 8 h, however exposure to 35 ppm is only secure for 10 min. In this work a brief introduction to ammonia aspects are presented, like its physical and chemical properties, the dangers in its manipulation, its ways of production and its sources. The application areas in which ammonia gas detection is important and needed are also referred: environmental gas analysis (e.g. intense farming), automotive-, chemical- and medical industries. In order to monitor ammonia gas in these different areas there are some requirements that must be attended. These requirements determine the choice of sensor and, therefore, several types of sensors with different characteristics were developed, like metal oxides, surface acoustic wave-, catalytic-, and optical sensors, indirect gas analyzers, and conducting polymers. All the sensors types are described, but more attention will be given to polyaniline (PANI), particularly to its characteristics, syntheses, chemical doping processes, deposition methods, transduction modes, and its adhesion to inorganic materials. Besides this, short descriptions of PANI nanostructures, the use of electrospinning in the formation of nanofibers/microfibers, and graphene and its characteristics are included. The created sensor is an instrument that tries to achieve a goal of the medical community in the control of the breath’s ammonia levels being an easy and non-invasive method for diagnostic of kidney malfunction and/or gastric ulcers. For that the device should be capable to detect different levels of ammonia gas concentrations. So, in the present work an ammonia gas sensor was developed using a conductive polymer composite which was immobilized on a carbon transducer surface. The experiments were targeted to ammonia measurements at ppb level. Ammonia gas measurements were carried out in the concentration range from 1 ppb to 500 ppb. A commercial substrate was used; screen-printed carbon electrodes. After adequate surface pre-treatment of the substrate, its electrodes were covered by a nanofibrous polymeric composite. The conducting polyaniline doped with sulfuric acid (H2SO4) was blended with reduced graphene oxide (RGO) obtained by wet chemical synthesis. This composite formed the basis for the formation of nanofibers by electrospinning. Nanofibers will increase the sensitivity of the sensing material. The electrospun PANI-RGO fibers were placed on the substrate and then dried at ambient temperature. Amperometric measurements were performed at different ammonia gas concentrations (1 to 500 ppb). The I-V characteristics were registered and some interfering gases were studied (NO2, ethanol, and acetone). The gas samples were prepared in a custom setup and were diluted with dry nitrogen gas. Electrospun nanofibers of PANI-RGO composite demonstrated an enhancement in NH3 gas detection when comparing with only electrospun PANI nanofibers. Was visible higher range of resistance at concentrations from 1 to 500 ppb. It was also observed that the sensor had stable, reproducible and recoverable properties. Moreover, it had better response and recovery times. The new sensing material of the developed sensor demonstrated to be a good candidate for ammonia gas determination.

Limit Cycle Prediction of Systems with Fractional Controllers and Backlash

This article investigates the limit cycle (LC) prediction of systems with backlash by means of the describing function (DF) when using discrete fractional-order (FO) algorithms. The DF is an approximate method that gives good estimates of LCs. The implementation of FO controllers requires the use of rational approximations, but such realizations produce distinct dynamic types of behavior. This study analyzes the accuracy in the prediction of LCs, namely their amplitude and frequency, when using several different algorithms. To illustrate this problem we use FO-PID algorithms in the control of systems with backlash.

Life Cycle Assessment of the Hybrid Vehicle – Toyota Prius

Die Luftverschmutzung, die globale Erwärmung sowie die Verknappung der endlichen Ressourcen sind die größten Bedenken der vergangenen Jahrzehnte. Die Nachfrage nach jeglicher Mobilität steigt rapide. Dementsprechend bemüht ist die Automobilindustrie Lösungen für Mobilität unter dem Aspekt der Nachhaltigkeit und dem Umweltschutz anzubieten. Die Elektrifizierung hat sich hierbei als der beste Weg herausgestellt, um die Umweltprobleme sowie die Abhängigkeit von fossilen Brennstoffen zu lösen. Diese Arbeit soll einen Einblick über die Umweltauswirkungen des Hybridfahrzeuges Toyota Prius geben. Hierbei findet eine Gliederung in vier verschiedene Lebensphasen statt. Im Anschluss bietet die Sachbilanz die Möglichkeit die Umweltauswirkungen mit verschiedenen Antriebsmöglichkeiten und Brennstoffen zu vergleichen. Das Modell hat gezeigt, dass der Toyota Prius während der Nutzung einen hohen Einfluss auf das Treibhauspotenzial aufweist. Durch die Nutzung anderer Brennstoffe, wie beispielsweise Ethanol oder Methanol lassen sich die Auswirkungen am Treibhauspotenzial sowie der Verbrauch an abiotischen Ressourcen reduzieren. Vergleicht man die Elektromobilität mit der konventionellen, so ist festzustellen, dass diese Art der Mobilität die derzeit beste Möglichkeit zur Reduzierung der Umweltbelastungen bietet. Die Auswirkungen der Elektromobilität sind im hohen Maße abhängig von der Art des verwendeten Strommixes.

Impacto Ambiental do Processo de Tingimento de uma Indústria de Curtumes e Avaliação do Desempenho da ETAR

Um dos objetivos desta dissertação de mestrado foi avaliar o impacto ambiental do processo de tingimento usado na indústria de curtumes, em termos de volume de efluente produzido e sua carga poluente. Pretendeu-se também encontrar alternativas ao nível do processo de tingimento que levem a uma melhoria na qualidade do efluente produzido. Outro objetivo deste trabalho foi avaliar o funcionamento da ETAR existente na empresa JR Fontes, no que diz respeito aos parâmetros em estudo (carência química de oxigénio - CQO, pH, crómio e teor de sólidos suspensos totais - SST), propondo alterações que permitam respeitar os valores de emissão exigidos na licença de descarga da empresa. Verificou-se que o processo de tingimento aplicado pela empresa JR Fontes é muito poluente, em termos de carga orgânica e matéria em suspensão. Este facto é comprovado pelos resultados obtidos para os três processos estudados: Montana, Galáctico e Navak. Todos os processos apresentam um efluente com pH ácido (aproximado a 3) e valores de CQO superiores a 3550 mg O2/L, sendo o processo Navak aquele que apresenta o valor mais alto para o banho composto, 8362 mg O2/L. Relativamente ao teor de crómio, o banho de recurtume com concentração mais elevada de crómio total é o banho 1 do processo Navak, com 2297 mg/L, sendo que a concentração destes banhos é sempre elevada, igual ou superior a 746 mg/L. No que diz respeito à matéria em suspensão, o processo Navak é novamente o mais poluente, com um valor de 3842 mg SST/L, não sendo obtidos nos outros processos, valores inferiores a 1205 mg SST/L. Na realização de um processo alternativo de tingimento verificou-se que é possível diminuir a carga orgânica do efluente originado. A aplicação de recurtumes sintéticos deu origem a efluentes menos poluentes. O melhor valor obtido para a CQO foi de 1113 mg O2/L, sendo obtidos valores não superiores a 7185 mg O2/L para processos de características semelhantes aos aplicados nesta indústria. Relativamente à ETAR, apesar das restrições ao funcionamento que esta apresenta, no geral pode ser considerada eficiente, embora não consiga atingir o objetivo pretendido de remoção para a CQO, ou seja o valor de 1100 mg O2/L. Nos restantes parâmetros é cumprido o limite de emissão (350 mg SST/L, pH entre 6 e 9 e 2 mg Cr/L para o crómio total): os SST apresentam o valor de 98 mg SST/L, o crómio total de 1,2 mg Cr/L e o pH encontra-se entre 8 e 9. São aqui feitas duas abordagens para solucionar os problemas existentes na ETAR. A primeira considera um ajuste no tratamento e equipamentos existentes, através da reconstrução do tanque de equalização, da substituição do coagulante por sulfato ferroso e da reconstrução do sedimentador, assim como a substituição das tubagens por umas de maior diâmetro, solucionando assim problemas de manutenção de toda a instalação e do incumprimento da legislação. A outra abordagem implica a substituição do sistema de afinação existente, os filtros de areia e carvão ativados, por um sistema de membranas de ultrafiltração ou por dois filtros de carvão ativado. Para tratar um efluente com um valor de CQO de 3000 mg O2/L com o carvão estudado, seriam necessários 132 kg de carvão por coluna, aproveitando-se os equipamentos existentes. No caso das membranas filtrantes, estas são eficazes, reduzindo a CQO em cerca de 70%. Ao contrário do carvão, a aplicação deste sistema implicaria a aquisição de novos equipamentos. Futuramente propõe-se a avaliação dos vários tipos de reagentes usados no tingimento de couro de forma a aplicar no tratamento aqueles que produzam as características desejadas no produto final e a que apresentem um menor resultado de CQO. Propõe-se também o estudo de viabilidade da remoção de crómio dos banhos de recurtume e consequente avaliação da aplicabilidade de um tratamento biológico em substituição ou como complemento do tratamento existente.

Sertraline accumulation and effects in the estuarine decapod Carcinusmaenas: Importance of the history of exposure to chemical stress

Sertraline is widely prescribed worldwide and frequently detected in aquatic systems. There is, however, a remarkable gap of information on its potential impact on estuarine and coastal invertebrates. This study investigated sertraline accumulation and effects in Carcinus maenas. Crabs from a moderately contaminated (Lima) and a low-impacted (Minho) estuary were exposed to environmental and high levels of sertraline (0.05, 5, 500 μg L−1). A battery of biomarkers related to sertraline mode of action was employed to assess neurotransmission, energy metabolism, biotransformation and oxidative stress pathways. After a seven-day exposure, sertraline accumulation in crabs’ soft tissues was found in Lima (5 μg L−1: 15.3 ng L−1 ww; 500 μg L−1: 1010 ng L−1 ww) and Minho (500 μg L−1: 605 ng L−1 ww) animals. Lima crabs were also more sensitive to sertraline than those from Minho, exhibiting decreased acetylcholinesterase activity, indicative of ventilatory and locomotory dysfunction, inhibition of anti-oxidant enzymes and increased oxidative damage at ≥0.05 μg L−1. The Integrated Biomarker Response (IBR) index indicated their low health status. In addition, Minho crabs showed non-monotonic responses of acetylcholinesterase suggestive of hormesis. The results pointed an influence of the exposure history on differential sensitivity to sertraline and the need to perform evaluations with site-specific ecological receptors to increase relevance of risk estimations when extrapolating from laboratory to field conditions.

Isoflavones in food supplements: chemical profile, label accordance and permeability study in Caco-2 cells

Consumers nowadays are playing an active role in their health-care. A special case is the increasing number of women, who are reluctant to use exogenous hormone therapy for the treatment of menopausal symptoms and are looking for complementary therapies. However, food supplements are not clearly regulated in Europe. The EFSA has only recently begun to address the issues of botanical safety and purity regulation, leading to a variability of content, standardization, dosage, and purity of available products. In this study, isoflavones (puerarin, daidzin, genistin, daidzein, glycitein, genistein, formononetin, prunetin, and biochanin A) from food supplements (n = 15) for menopausal symptoms relief are evaluated and compared with the labelled information. Only four supplements complied with the recommendations made by the EC on the tolerable thresholds. The intestinal bioavailability of these compounds was investigated using Caco-2 cells. The apparent permeability coefficients of the selected isoflavonoids across the Caco-2 cells were affected by the isoflavone concentration and product matrix.

Valorização da Drêche Cervejeira: Fermentação de Pentoses

O presente trabalho tem como objetivo a otimização da etapa de fermentação dos açúcares obtidos a partir da drêche cervejeira para produção do bioetanol através da utilização das leveduras Pichia stipitis NCYC 1541 e Kluyveromyces marxianus NCYC 2791 como agentes fermentativos. O meio de cultura usado para manter as culturas destas leveduras foi Yeast Extract Peptone Dextrose (YEPD). O principal propósito deste trabalho foi o de encontrar alternativas aos combustíveis fósseis, pautando-se por soluções inofensivas para o meio ambiente e sustentáveis. Assim, o trabalho está dividido em quatro etapas: 1) caraterização química e biológica da drêche; 2) pré-tratamento ácido e hidrólise enzimática para primeiramente quebrar as moléculas de lenhina que envolvem os polímeros de celulose e hemicelulose e em seguida romper as ligações poliméricas destas macromoléculas por ação enzimática e transforma-las em açúcares simples, respetivamente, obtendo-se então a glucose, a maltose, a xilose e a arabinose; e, por último, 3) otimização da etapa de fermentação da glucose, maltose e das pentoses que constitui a condição essencial para se chegar à síntese do bioetanol de um modo eficiente e sustentável e 4) a recuperação do bioetanol produzido por destilação fracionada. A quantificação dos açúcares libertados no processo foi feita recorrendo a análises por cromatografia líquida de alta eficiência (HPLC). Neste estudo foram identificados e quantificados cinco açúcares: Arabinose, Glucose, Maltose, Ribose e Xilose. Na etapa de pré-tratamento e hidrólise enzimática foram usados os ácidos clorídrico (HCl) e nítrico (HNO3) com a concentração de 1% (m/m), e as enzimas Glucanex 100g e Ultraflo L. Foram testadas seis condições de pré-tratamento e hidrólise enzimática, alterando os parâmetros tempo de contacto e razão enzimas/massa de drêche, respetivamente, e mantendo a temperatura (50 ºC), velocidade de agitação (75 rpm) e concentração dos ácidos (1% (m/m)). No processamento de 25 g de drêche seca com 0,5 g de Glucanex, 0,5 mL de Ultraflo e um tempo de reação de 60 minutos para as enzimas foi obtida uma eficiência de 15%, em hidrolisado com 6% da celulose. Realizou-se a fermentação do hidrolisado resultante do pré-tratamento ácido e hidrólise enzimática de drêche cervejeira e de meios sintéticos preparados com os açúcares puros, usando as duas estirpes selecionadas para este estudo: Pichia stipitis NCYC 1541 e Kluyveromyces marxianus NYCY 2791. As eficiências de fermentação dos açúcares nos meios sintéticos foram superiores a 80% para ambas as leveduras. No entanto, as eficiências de fermentação do hidrolisado da drêche foram de 45,10% pela Pichia stipitis e de 36,58 para Kluyveromyces marxianus, para um tempo de fermentação de 72 horas e à temperatura de 30 °C. O rendimento teórico em álcool no hidrolisado da drêche é de 0,27 g/g, três vezes maior do que o real (0,0856 g/g), para Pichia stipitis e de 0,19 g/g seis vezes maior do que o real (0,0308 g/g), para a Kluyveromyces marxianus.