NMR in the characterization of heavy residual procedural streams

The main objective of this work was to monitor a set of physical-chemical properties of heavy oil procedural streams through nuclear magnetic resonance spectroscopy, in order to propose an analysis procedure and online data processing for process control. Different statistical methods which allow to relate the results obtained by nuclear magnetic resonance spectroscopy with the results obtained by the conventional standard methods during the characterization of the different streams, have been implemented in order to develop models for predicting these same properties. The real-time knowledge of these physical-chemical properties of petroleum fractions is very important for enhancing refinery operations, ensuring technically, economically and environmentally proper refinery operations. The first part of this work involved the determination of many physical-chemical properties, at Matosinhos refinery, by following some standard methods important to evaluate and characterize light vacuum gas oil, heavy vacuum gas oil and fuel oil fractions. Kinematic viscosity, density, sulfur content, flash point, carbon residue, P-value and atmospheric and vacuum distillations were the properties analysed. Besides the analysis by using the standard methods, the same samples were analysed by nuclear magnetic resonance spectroscopy. The second part of this work was related to the application of multivariate statistical methods, which correlate the physical-chemical properties with the quantitative information acquired by nuclear magnetic resonance spectroscopy. Several methods were applied, including principal component analysis, principal component regression, partial least squares and artificial neural networks. Principal component analysis was used to reduce the number of predictive variables and to transform them into new variables, the principal components. These principal components were used as inputs of the principal component regression and artificial neural networks models. For the partial least squares model, the original data was used as input. Taking into account the performance of the develop models, by analysing selected statistical performance indexes, it was possible to conclude that principal component regression lead to worse performances. When applying the partial least squares and artificial neural networks models better results were achieved. However, it was with the artificial neural networks model that better predictions were obtained for almost of the properties analysed. With reference to the results obtained, it was possible to conclude that nuclear magnetic resonance spectroscopy combined with multivariate statistical methods can be used to predict physical-chemical properties of petroleum fractions. It has been shown that this technique can be considered a potential alternative to the conventional standard methods having obtained very promising results.

Ecological quality assessment in transitional systems

Estuaries are poles of attraction for human settlement which is a source of pressures to surface water bodies. The implementation of the European Water Framework Directive (WDF, 2000/60/EC) has increased the investigation in order to develop methodologies to assess the Ecological Quality Status (EQS) of aquatic ecosystems. Transitional systems are naturally stressed and characterized by highly dynamic physical, chemical and hydro-morphologic conditions and by species with a higher level of tolerance to change, being more difficult to develop suitable quality indicators for these systems. The general purpose of this study is to test the ability of synthesis descriptors, including primary (S, taxa richness) and derived biological variable (H’, Shannon-Wiener diversity), biotic indices (AMBI and M-AMBI), body size properties (abundance distribution by body size classes, length, weight and length-weight relationships) and non-taxonomic indices (ISS), as well as functional indicators related to the decomposition rates of various experimental substrates, a macrophyte (Phragmites australis) and an alga (Fucus vesiculosus), to evaluate the environmental quality in transitional systems. This study was carried out in one of the most pristine channels of the Ria the Aveiro, Mira Channel, along a full salinity gradient and in a metals and metalloid sediment contamination area, the Estarreja Channel, and two reference channels (Canelas and Salreu). In this study were used different sampling techniques, the leaf-bag technique and a hand-held corer. In Mira Channel, the alga and the macrophyte presented an opposite trend in the decomposition rate along the salinity gradient, with the decomposition rates of the alga always higher than those of the macrophyte. The decomposition rates of the macrophyte and the alga were higher in the mid estuary and in higher salinity areas, respectively, corresponding to the preferencial distribution areas of each species. The macrobenthic fauna associated with the decaying and an artificial substrate (control) showed equally well the benthic succession from the marine to the freshwater areas and, despite the strong differences in the decay rates, no significant differences were found between the benthic communities associated with the alga and the macrophyte. The body size properties of the macrobenthic fauna associated with the P. australis leaf-bag (1mm and 5mm) and corer samples were studied along the full salinity gradient. The dominant species of the sub-set of measured specimens were not the same of the original macrobenthic fauna sampled but, despite that, the sub-set of measured specimens was also able to show the benthic succession from the marine to the freshwater areas. The body size abundance distribution of the benthic macroinvertebrates according to the ISS size classes did not show a particular trend in any sampler along the salinity gradient. Significant differences were found in the length, weight and length-weight relationships of Annelids, , Molluscs and even some species along the salinity gradient. No significant differences were found in the AMBI, M-AMBI and ISS values along the salinity gradient for all the samplers. The EQS of the corer samples obtained using the M-AMBI was lower than that of the leaf-bags. The EQS obtained with the ISS was higher than that obtained with the M-AMBI in the leaf-bags but not in the corer samples. The ecological effects of contaminated sediments associated with the industrial chemical effluents discharged in the Estarreja Channel were studied a decade after ceasing the emissions, using the Sediment Quality Triad approach and two reference channels. The results showed that despite the emissions ceased in 2004, the sediment remains polluted with high levels of metals and metalloid, available to bioaccumulation and with severe consequences at the community level. The sediment contamination problem was also studied using the leaf-bag technique with a macrophyte, an alga and a control substrate. The results showed that the decay rates, the associated macrofauna and the application of the AMBI, M-AMBI and ISS indices to the mesh-bag samples were not able to identify the sediment contamination. Contrarily to the AMBI, the M-AMBI and the ISS showed significant differences between the contaminated and the reference channels for the corer samples. Although such statistical significance, the interest of using these complex biotic indices could be questioned, when much simple ones, like the S and H’ allow to reach the same conclusions.

Benthic biotope index for classifying estuarine habitats

An integration of sediment physical, chemical, biological, and toxicity data is necessary for a meaningful interpretation of the complex sediment conditions in the marine environment. Assessment of benthic community is a vital component for that interpretation, yet their evaluation is complex and requires a large expenditure of time and funds. Thus, there is a need for new tools that are less expensive and more understandable for managers. This paper presents a benthic biotope index to predict from physical and chemical variables the occurrence of macrobenthic habitats, applied to Sado Estuary, as a case of study.

Traditional algarvian distillats and liqueurs historic scientific aspects

All the evidence indicates that distillation and liqueurs preparation began in Monchique mountain because this place was pointed as a possible capital of the oldest population of Algarve and an important Arabic village (Barreto, 1972: 19). It was possible to find lots of vestiges like the alembic produced by Arabic population near the X century (Telo, 1988: 77). Traditionally the Algarvian people produce the Arbutus unedo L., fig, carob, grape distillates. At the same time they produce liqueur-using maceration of parts of plants or fruits in some kinds of distillates. Most of the work about Algarvian distillates started by studying the basic compounds of Arbutus unedo spirits by gas chromatography (GC) and mass spectrometry (MS) as well as other physical-chemical properties. In a second phase aged distillates were studied by their phenolic compounds evolution using high resolution liquid chromatography (HPLC). Volatile compounds of traditional liqueurs were identified by head space micro extraction solid phase (HE-SPME) and also analysed by gas chromatography mass spectrometry (GC-MS) and when possible confirmed with standards. Total phenols were determined by Folin-Ciocalteur method. Flavenoids were studied by high performance liquid chromatography (HPLC). Sensorial analysis was also done in every drink studies. The results showed that the arbutus distillate doesn’t present a high level of methanol according to the current legislation. The excesses of acidity or ethyl acetate present normal values when the fermentation is well done (Galego, et al. 1995: 341; Galego, et al. 1995: 685). During the aging process, the colour of spirits tend to become darker, the colour changes occurred more rapidly in the arbutus spirits located in cellars with higher temperatures (Galego, et al. 2001: 432). In the sensory evaluation of samples aged during 12 months into 50 L medium toasting level oak wood barrels, panellists considered that samples of arbutus spirit had too much wood flavour and they were not able to detect the characteristic aroma of arbutus fruit (Galego, et al., 2001: 183). Differences in liqueurs were observed using HS-SPME-GC, HS-SPME-GC-MS or HPLC analysis and this observation was confirmed by a sensorial panel (Galego, et al. 2003: 60).

Machine learning methods for quantitative structure-property relationship modeling

Tese de doutoramento, Informática (Bioinformática), Universidade de Lisboa, Faculdade de Ciências, 2014

Incorporação de resíduos cerâmicos em argamassas de cal aérea sujeitas a condições severas de humidade e salinidade

Trabalho Final de Mestrado para obtenção do grau de Mestre em Engenharia Civil na Área de Especialização de Edificações

Contribuição para o conhecimento sobre o efeito da utilização de material pozolânico no fabrico de betão

O presente trabalho, realizado no âmbito da Tese de Mestrado, tem como principal objectivo estudar as características pozolânicas dos materiais da zona de Arganil para substituição parcial do cimento Portland com o objectivo de intensificar certas qualidades devido à diminuição da porosidade do betão. Estas qualidades são interessantes quando se procura maior durabilidade. Para tal, foram realizados diversos ensaios para a caracterização física, química e mineralógica dos produtos. Os metacaulinos utilizados foram obtidos de amostras de argila submetidas a calcinação (750oC, durante uma hora), processo que permitiu a desidroxilação quase total da matéria-prima, transformando esta numa fase amorfa e irreversível, com propriedades pozolânicas. São apresentados os resultados dos ensaios de caracterização da matéria-prima, das condições de calcinação e do produto resultante da desidroxilação, nomeadamente a determinação da pozolanicidade e superfície específica e das características fundamentais para a aplicabilidade do produto. Descreve ainda o emprego do metacaulino em betões de resistência convencional. Estudou-se a influência do emprego do metacaulino (15% de substituição de cimento, em massa) na resistência à flexão e à compressão (aos 28 dias) em argamassas e o emprego de metacaulino (10%, 15% e 20% de substituição de cimento, em massa) na resistência à compressão (3, 7 e 28 dias) no betão.

Formulação de um biofilme para controlo da listéria em queijos

Dissertação de Mestrado, Tecnologia e Segurança Alimentar, 12 Fevereiro de 2016, Universidade dos Açores.

Electrochemical oxidation of propanil and related N-substituted amides

The electrochemical behaviour of propanil and related N-substituted amides (acetanilide and N,N-diphenylacetamide) was studied by cyclic and square wave voltammetry using a glassy carbon electrode. Propanil has been found to have chemical stability under the established analytical conditions and showed an oxidation peak at +1.27V versus Ag/AgCl at pH 7.5. N,N-diphenylacetamide has a higher oxidation potential than the other compounds of +1.49V versus Ag/AgCl. Acetanilide oxidation occurred at a potential similar to that of propanil, +1.24V versus Ag/AgCl. These results are in agreement with the substitution pattern of the nitrogen atom of the amide. A degradation product of propanil, 3,4-dichloroaniline (DCA), was also studied, and showed an oxidation peak at +0.66V versus Ag/AgCl. A simple and specific quantitative electroanalytical method is described for the analysis of propanil in commercial products that contain propanil as the active ingredient, used in the treatment of rice crops in Portugal.

Soil sampling design and sampling techniques for soil properties monitoring – common difficulties related to forest soils

Mathematical models and statistical analysis are key instruments in soil science scientific research as they can describe and/or predict the current state of a soil system. These tools allow us to explore the behavior of soil related processes and properties as well as to generate new hypotheses for future experimentation. A good model and analysis of soil properties variations, that permit us to extract suitable conclusions and estimating spatially correlated variables at unsampled locations, is clearly dependent on the amount and quality of data and of the robustness techniques and estimators. On the other hand, the quality of data is obviously dependent from a competent data collection procedure and from a capable laboratory analytical work. Following the standard soil sampling protocols available, soil samples should be collected according to key points such as a convenient spatial scale, landscape homogeneity (or non-homogeneity), land color, soil texture, land slope, land solar exposition. Obtaining good quality data from forest soils is predictably expensive as it is labor intensive and demands many manpower and equipment both in field work and in laboratory analysis. Also, the sampling collection scheme that should be used on a data collection procedure in forest field is not simple to design as the sampling strategies chosen are strongly dependent on soil taxonomy. In fact, a sampling grid will not be able to be followed if rocks at the predicted collecting depth are found, or no soil at all is found, or large trees bar the soil collection. Considering this, a proficient design of a soil data sampling campaign in forest field is not always a simple process and sometimes represents a truly huge challenge. In this work, we present some difficulties that have occurred during two experiments on forest soil that were conducted in order to study the spatial variation of some soil physical-chemical properties. Two different sampling protocols were considered for monitoring two types of forest soils located in NW Portugal: umbric regosol and lithosol. Two different equipments for sampling collection were also used: a manual auger and a shovel. Both scenarios were analyzed and the results achieved have allowed us to consider that monitoring forest soil in order to do some mathematical and statistical investigations needs a sampling procedure to data collection compatible to established protocols but a pre-defined grid assumption often fail when the variability of the soil property is not uniform in space. In this case, sampling grid should be conveniently adapted from one part of the landscape to another and this fact should be taken into consideration of a mathematical procedure.

Multiple linear and principal component regressions for modelling ecotoxicity bioassay response

The ecotoxicological response of the living organisms in an aquatic system depends on the physical, chemical and bacteriological variables, as well as the interactions between them. An important challenge to scientists is to understand the interaction and behaviour of factors involved in a multidimensional process such as the ecotoxicological response.With this aim, multiple linear regression (MLR) and principal component regression were applied to the ecotoxicity bioassay response of Chlorella vulgaris and Vibrio fischeri in water collected at seven sites of Leça river during five monitoring campaigns (February, May, June, August and September of 2006). The river water characterization included the analysis of 22 physicochemical and 3 microbiological parameters. The model that best fitted the data was MLR, which shows: (i) a negative correlation with dissolved organic carbon, zinc and manganese, and a positive one with turbidity and arsenic, regarding C. vulgaris toxic response; (ii) a negative correlation with conductivity and turbidity and a positive one with phosphorus, hardness, iron, mercury, arsenic and faecal coliforms, concerning V. fischeri toxic response. This integrated assessment may allow the evaluation of the effect of future pollution abatement measures over the water quality of Leça River.

Optimization of River Water Quality Surveys by Multivariate Analysis of Physicochemical, Bacteriological and Ecotoxicological Data

This study aims to optimize the water quality monitoring of a polluted watercourse (Leça River, Portugal) through the principal component analysis (PCA) and cluster analysis (CA). These statistical methodologies were applied to physicochemical, bacteriological and ecotoxicological data (with the marine bacterium Vibrio fischeri and the green alga Chlorella vulgaris) obtained with the analysis of water samples monthly collected at seven monitoring sites and during five campaigns (February, May, June, August, and September 2006). The results of some variables were assigned to water quality classes according to national guidelines. Chemical and bacteriological quality data led to classify Leça River water quality as “bad” or “very bad”. PCA and CA identified monitoring sites with similar pollution pattern, giving to site 1 (located in the upstream stretch of the river) a distinct feature from all other sampling sites downstream. Ecotoxicity results corroborated this classification thus revealing differences in space and time. The present study includes not only physical, chemical and bacteriological but also ecotoxicological parameters, which broadens new perspectives in river water characterization. Moreover, the application of PCA and CA is very useful to optimize water quality monitoring networks, defining the minimum number of sites and their location. Thus, these tools can support appropriate management decisions.

Caracterização física e química de fíleres para fabrico de misturas betuminosas

Mestrado em Engenharia Geotécnica e Geoambiente

Bioatividade de Líquidos Iónicos derivados do Ácido Valpróico em bactérias Gram-negativa

Os Líquidos Iónicos (LIs) são sais orgânicos constituídos exclusivamente por iões e possuem pontos de fusão inferiores a 100ºC. As suas propriedades únicas e o facto de ser possível ajustar as suas propriedades físicas, químicas e biológicas, de acordo com o objetivo pretendido, tornam esta classe de compostos, um grande objeto de estudo de inúmeros investigadores. Desde os inícios da sua aplicação até à atualidade, a investigação nesta área expandiu o seu raio de ação, estando já descrito o seu potencial como agentes antimicrobianos e, mais recentemente, como compostos farmacêuticos ativos. Atualmente muitas das suas aplicações são baseadas nas suas propriedades biológicas. Esta Tese teve como objetivo avaliar a influência que os LIs podem exercer a nível do crescimento bacteriano e estudar alternativas de combater a resistência bacteriana. Todos os LIs utilizados neste trabalho tinham como anião o ácido valpróico, sendo utilizados catiões orgânicos de amónio e de imidazólio. Foram utilizadas 4 bactérias e avaliou-se a atividade biológica e a respetiva taxa de crescimento. O estudo da sua atividade biológica foi feito através da determinação da Concentração Mínima Inibitória (CMI) e a análise das suas curvas de crescimentos na presença e ausência de composto. Com este trabalho foi possível verificar que dentro dos compostos em estudo, LIs derivados do valproato, o Valproato com o cetilperidínio [valp] [cetylpir] foi o que influenciou o crescimento de todas as bactérias estudadas. Este estudo demonstrou o potencial antibacteriano de alguns compostos, podendo desta forma vir a ser utilizados para fins farmacêuticos

Previsão de avarias em transformadores de potência através da análise de ensaios físico-químicos

Os Transformadores de potência são máquinas de elevada importância ao nível dos Sistemas Elétricos de Energia (SEE) uma vez que são estas máquinas que possibilitam a interligação dos diferentes níveis de tensão da rede e a transmissão de energia elétrica em Corrente Alternada (CA). Geralmente, estas máquinas são de grandes dimensões e de elevado nível de complexidade construtiva. Caracterizam-se por possuírem períodos de vida útil bastante elevados (vinte a trinta anos) e preços elevados, o que conduz a um nível de exigência de fiabilidade muito elevada, uma vez que não e viável a existência de muitos equipamentos de reserva nos SEE. Com o objetivo de tentar maximizar o período de vida útil dos transformadores de potência e a sua fiabilidade, tenta-se, cada vez mais, implementar conceitos de manutenção preventiva a este tipo de máquinas. No entanto, a gestão da sua vida útil e extremamente complexa na medida em que, estas máquinas têm vários componentes cruciais e suscetiveis de originar falhas e, quase todos eles, encontram-se no interior de uma cuba. Desta forma, não e possível obter uma imagem do seu estado, em tempo real, sem colocar o transformador fora de serviço, algo que acarreta custos elevados. Por este motivo, desenvolveu-se uma técnica que permite obter uma indicação do estado do transformador, em tempo real, sem o retirar de serviço, colhendo amostras do óleo isolante e procedendo a sua análise físico-química e Analise Gases Dissolvidos (DGA). As análises aos óleos isolantes tem vindo a adquirir uma preponderância muito elevada no diagnóstico de falhas e na analise do estado de conservação destes equipamentos tendo-se desenvolvido regras para interpretação dos parâmetros dos óleos com carácter normativo. Considerando o conhecimento relativo a interpretação dos ensaios físico-químicos e DGA ao oleol, e possível desenvolver ferramentas capazes de otimizar essas mesmas interpretações e aplicar esse conhecimento no sentido de prever a sua evolução, assim como o surgimento de possíveis falhas em transformadores, para assim otimizar os processos de manutenção. Neste campo as Redes Neuronais Artificiais (RNAs) têm um papel fundamental