Response surface methodology applied to SPE for the determination of ibuprofen in various types of water samples

Over the last few years, there has been a growing concern about the presence of pharmaceuticals in the environment. The main objective of this study was to develop and validate an SPE method using surface response methodology for the determination of ibuprofen in different types of water samples. The influence of sample pH and sample volume on the ibuprofen recovery was studied. The effect of each studied independent variable is pronounced on the dependent variable (ibuprofen recovery). Good selectivity, extraction efficiency, and precision were achieved using 600 mL of sample volume with the pH adjusted to 2.2. LC with fluorescence detection was employed. The optimized method was applied to 20 water samples from the North and South of Portugal.

Multidimensional scaling analysis of the dynamics of a country economy

This paper analyzes the Portuguese short-run business cycles over the last 150 years and presents the multidimensional scaling (MDS) for visualizing the results. The analytical and numerical assessment of this long-run perspective reveals periods with close connections between the macroeconomic variables related to government accounts equilibrium, balance of payments equilibrium, and economic growth. The MDS method is adopted for a quantitative statistical analysis. In this way, similarity clusters of several historical periods emerge in the MDS maps, namely, in identifying similarities and dissimilarities that identify periods of prosperity and crises, growth, and stagnation. Such features are major aspects of collective national achievement, to which can be associated the impact of international problems such as the World Wars, the Great Depression, or the current global financial crisis, as well as national events in the context of broad political blueprints for the Portuguese society in the rising globalization process.

Recuperação parcial da água de lavagem dos filtros utilizados no tratamento da água de piscinas de uso público

Mestrado em Engenharia Química. Ramo optimização energética na indústria química

Sustentabilidade na reablitação urbana

A indústria da construção é um setor com grande impacto na economia, no Produto Interno Bruto (PIB) e ainda em postos de trabalho diretos e indiretos. No entanto, é um dos setores com maior impacte ambiental. Com a crise económica e financeira que o país atravessa, este setor foi um dos mais afetados, contribuindo para o aumento do desemprego visto tratar-se do setor com maior taxa de empregabilidade. Concomitantemente, ocorre saturação do mercado com a construção nova e desertificação dos centros urbanos com a degradação das habitações. Assim, como impulsionador da economia, surge a aposta na reabilitação do parque edificado que, com a legislação em vigor e com os incentivos dados pela tutela tem tudo para impulsionar o setor. Sabendo que a indústria da construção é um dos setores com maiores impactes ambientais, faz todo o sentido reabilitar-se de uma forma mais sustentável. Aplicando os princípios da sustentabilidade a todo o ciclo de vida do edifício, conseguimos reduzir os recursos na fase de construção (resíduos de construção) e na fase de exploração (consumo de energia e de água). Podemos ainda reduzir os custos de energia para climatização ao termos em conta a orientação do edifício e a envolvente, os recursos naturais e aplicando tecnologias solares passivas. Assim, ao aplicarmos os princípios da construção sustentável na reabilitação urbana podemos diminuir os impactes ambientais, a produção de CO2, as emissões de gases com efeito de estufa, os resíduos de construção e a área impermeabilizada.

Practical software improve design and performance of a randomly packed air stripping column for removing volatile organic compounds from water

STRIPPING is a software application developed for the automatic design of a randomly packing column where the transfer of volatile organic compounds (VOCs) from water to air can be performed and to simulate it’s behaviour in a steady-state. This software completely purges any need of experimental work for the selection of diameter of the column, and allows a choice, a priori, of the most convenient hydraulic regime for this type of operation. It also allows the operator to choose the model used for the calculation of some parameters, namely between the Eckert/Robbins model and the Billet model for estimating the pressure drop of the gaseous phase, and between the Billet and Onda/Djebbar’s models for the mass transfer. Illustrations of the graphical interface offered are presented.

Sustainable Development Action Plan at ISEP - From Concept to Engineering Practice

Some of the main challenges in Incorporating Sustainable Development practices into Engineering Education reside in establishing the bridge between concept and application. In particular the relation between value creation and the knowledge economy, innovation and entrepreneurship, as the main vehicles to a relevant application of the sustainable development concept, is not yet part of the majority of the engineering curricula in schools. Porto Polytechnical Engineering School (ISEP), a Global Reporting Initiative training partner in Portugal, as just presented its Sustainable Development Action Plan, with the main objective of creating a new kind of engineers, with Sustainable Development at the core of their degrees. The plan has several issues like publish an annual sustainability report, sustainable buildings, minimization of energy consumption and water policy, waste management, sustainable mobility, green procurement, EMAS certification, research and postgraduate activity and promotion of lectures and seminars in Sustainable Development.

Optimization of HS-SPME analytical conditions using factorial design for trihalomethanes determination in swimming pool water samples

Trihalomethanes (THMs) are widely referred and studied as disinfection by-products (DBPs). The THMs that are most commonly detected are chloroform (TCM), bromodichloromethane (BDCM), chlorodibromomethane (CDBM), and bromoform (TBM). Several studies regarding the determination of THMs in swimming pool water and air samples have been published. This paper reviews the most recent work in this field, with a special focus on water and air sampling, sample preparation and analytical determination methods. An experimental study has been developed in order to optimize the headspace solid-phasemicroextraction (HS-SPME) conditions of TCM, BDCM, CDBM and TBM from water samples using a 23 factorial design. An extraction temperature of 45 °C, for 25min, and a desorption time of 5 min were found to be the best conditions. Analysis was performed by gas chromatography with an electron capture detector (GC-ECD). The method was successfully applied to a set of 27 swimming pool water samples collected in the Oporto area (Portugal). TCM was the only THM detected with levels between 4.5 and 406.5 μg L−1. Four of the samples exceeded the guideline value for total THMs in swimming pool water (100 μgL−1) indicated by the Portuguese Health Authority.

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.

An uncertainty and sensitivity analysis applied to the prioritisation of pharmaceuticals as surface water contaminants from wastewater treatment plant direct emissions

In this study, the concentration probability distributions of 82 pharmaceutical compounds detected in the effluents of 179 European wastewater treatment plants were computed and inserted into a multimedia fate model. The comparative ecotoxicological impact of the direct emission of these compounds from wastewater treatment plants on freshwater ecosystems, based on a potentially affected fraction (PAF) of species approach, was assessed to rank compounds based on priority. As many pharmaceuticals are acids or bases, the multimedia fate model accounts for regressions to estimate pH-dependent fate parameters. An uncertainty analysis was performed by means of Monte Carlo analysis, which included the uncertainty of fate and ecotoxicity model input variables, as well as the spatial variability of landscape characteristics on the European continental scale. Several pharmaceutical compounds were identified as being of greatest concern, including 7 analgesics/anti-inflammatories, 3 β-blockers, 3 psychiatric drugs, and 1 each of 6 other therapeutic classes. The fate and impact modelling relied extensively on estimated data, given that most of these compounds have little or no experimental fate or ecotoxicity data available, as well as a limited reported occurrence in effluents. The contribution of estimated model input variables to the variance of freshwater ecotoxicity impact, as well as the lack of experimental abiotic degradation data for most compounds, helped in establishing priorities for further testing. Generally, the effluent concentration and the ecotoxicity effect factor were the model input variables with the most significant effect on the uncertainty of output results.

Otimização da extração sólido-líquido de antioxidantes de subprodutos florestais pelo método de superfície de resposta

Portugal continental apresenta uma vasta área florestal, que representa cerca de 35,4% da ocupação total do solo, com predominância de espécies como o eucalipto (Eucalyptus globulus) e o pinheiro-bravo (Pinus pinaster). Estas espécies apresentam uma elevada importância a nível económico, designadamente devido à sua ampla utilização, nomeadamente na indústria de celulose e papel, gerando elevadas quantidades de resíduos. Este resíduo de biomassa florestal é utilizado, na sua totalidade, para a geração de energia, na forma de eletricidade ou aquecimento. No entanto, existem outras opções viáveis, a nível económico, tais como a valorização destes subprodutos como fonte de compostos polifenólicos tornando-os, assim, um produto de valor acrescentado. A extração de compostos fenólicos de subprodutos florestais, como folhas de eucalipto e agulhas de pinheiros tem vindo a aumentar devido, principalmente, à substituição de antioxidantes sintéticos, contribuindo para a valorização de subprodutos florestais. Contudo, apesar de todas as potenciais aplicações e vantagens, apenas algumas centenas de espécies aromáticas identificadas são utilizadas à escala comercial. Neste trabalho foi avaliada a capacidade antioxidante de subprodutos da floresta, otimizando as condições de extração através do estudo dos fatores: tempo de extração, temperatura e composição de solvente através do método de superfície de resposta. O planeamento experimental utilizado teve como base um planeamento de compósito central e a avaliação do perfil de antioxidantes das matrizes analisadas foi realizada através de métodos de quantificação total, como o teor fenólico total, a atividade anti-radicalar – método do DPPH (radical 2,2-difenil-1-picrilhidrazilo) e o método de FRAP. Estes métodos analíticos convencionais foram modificados e, devidamente validados, para a análise em leitor de microplacas. Verificou-se que os extratos de pinheiro e de eucalipto, tanto as amostras verdes com as amostras, apresentam uma promissora capacidade antioxidante. O planeamento fatorial aplicado permitiu otimizar as condições de extração em relação às matrizes verdes. Contudo, o mesmo não se verificou em relação às matrizes secas. A composição (% de água) é sem dúvida o fator com mais efeito em todas as amostras (coeficientes de primeira e segunda ordem no modelo). Também a temperatura foi identificada como um fator com efeito significativo sobre os sistemas em análise.

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.

Early physiological and biochemical responses of rice seedlings to low concentration of microcystin-LR

Microcystin-leucine and arginine (microcystin- LR) is a cyanotoxin produced by cyanobacteria like Microcystis aeruginosa, and it’s considered a threat to water quality, agriculture, and human health. Rice (Oryzasativa) is a plant of great importance in human food consumption and economy, with extensive use around the world. It is therefore important to assess the possible effects of using water contaminated with microcystin-LR to irrigate rice crops, in order to ensure a safe, high quality product to consumers. In this study, 12 and 20-day-old plants were exposed during 2 or 7 days to a M. aeruginosa extract containing environmentally relevant microcystin-LR concentrations, 0.26–78 lg/L. Fresh and dry weight of roots and leaves, chlorophyll fluorescence, glutathione S-transferase and glutathione peroxidase activities, and protein identification by mass spectrometry through two-dimensional gel electrophoresis from root and leaf tissues, were evaluated in order to gauge the plant’s physiological condition and biochemical response after toxin exposure. Results obtained from plant biomass, chlorophyll fluorescence, and enzyme activity assays showed no significant differences between control and treatment groups. How- ever, proteomics data indicates that plants respond to M. aeruginosa extract containing environmentally relevant microcystin-LR concentrations by changing their metabolism, responding differently to different toxin concentrations. Biological processes most affected were related to protein folding and stress response, protein biosynthesis, cell signalling and gene expression regulation, and energy and carbohydrate metabolism which may denote a toxic effect induced by M. aeruginosa extract and microcystin- LR. Theimplications of the metabolic alterations in plant physiology and growth require further elucidation.

A DCAP for the social and solidarity economy

This article presents a work-in-progress version of a Dublin Core Application Profile (DCAP) developed to serve the Social and Solidarity Economy (SSE). Studies revealed that this community is interested in implementing both internal interoperability between their Web platforms to build a global SSE e-marketplace, and external interoperability among their Web platforms and external ones. The Dublin Core Application Profile for Social and Solidarity Economy (DCAP-SSE) serves this purpose. SSE organisations are submerged in the market economy but they have specificities not taken into account in this economy. The DCAP-SSE integrates terms from well-known metadata schemas, Resource Description Framework (RDF) vocabularies or ontologies, in order to enhance interoperability and take advantage of the benefits of the Linked Open Data ecosystem. It also integrates terms from the new essglobal RDF vocabulary which was created with the goal to respond to the SSE-specific needs. The DCAP-SSE also integrates five new Vocabulary Encoding Schemes to be used with DCAP-SSE properties. The DCAP development was based on a method for the development of application profiles (Me4MAP). We believe that this article has an educational value since it presents the idea that it is important to base DCAP developments on a method. This article shows the main results of applying such a method.

Recycling old screen-printed electrodes with newly designed plastic antibodies on the wall of carbon nanotubes as sensory element for in situ detection of bacterial toxins in water

Using low cost portable devices that enable a single analytical step for screening environmental contaminants is today a demanding issue. This concept is here tried out by recycling screen-printed electrodes that were to be disposed of and by choosing as sensory element a low cost material offering specific response for an environmental contaminant. Microcystins (MCs) were used as target analyte, for being dangerous toxins produced by cyanobacteria released into water bodies. The sensory element was a plastic antibody designed by surface imprinting with carefully selected monomers to ensure a specific response. These were designed on the wall of carbon nanotubes, taking advantage of their exceptional electrical properties. The stereochemical ability of the sensory material to detect MCs was checked by preparing blank materials where the imprinting stage was made without the template molecule. The novel sensory material for MCs was introduced in a polymeric matrix and evaluated against potentiometric measurements. Nernstian response was observed from 7.24 × 10−10 to 1.28 × 10−9 M in buffer solution (10 mM HEPES, 150 mM NaCl, pH 6.6), with average slopes of −62 mVdecade−1 and detection capabilities below 1 nM. The blank materials were unable to provide a linear response against log(concentration), showing only a slight potential change towards more positive potentials with increasing concentrations (while that ofthe plastic antibodies moved to more negative values), with a maximum rate of +33 mVdecade−1. The sensors presented good selectivity towards sulphate, iron and ammonium ions, and also chloroform and tetrachloroethylene (TCE) and fast response (<20 s). This concept was successfully tested on the analysis of spiked environmental water samples. The sensors were further applied onto recycled chips, comprehending one site for the reference electrode and two sites for different selective membranes, in a biparametric approach for “in situ” analysis.

Novel optical PVC probes for on-site detection/determination of fluoroquinolones in a solid/liquid interface: Application to the determination of Norfloxacin in aquaculture water

A novel optical disposable probe for screening fluoroquinolones in fish farming waters is presented, having Norfloxacin (NFX) as target compound. The colorimetric reaction takes place in the solid/liquid interface consisting of a plasticized PVC layer carrying the colorimetric reagent and the sample solution. NFX solutions dropped on top of this solid-sensory surface provided a colour change from light yellow to dark orange. Several metals were tested as colorimetric reagents and Fe(III) was selected. The main parameters affecting the obtained colour were assessed and optimised in both liquid and solid phases. The corresponding studies were conducted by visible spectrophotometry and digital image acquisition. The three coordinates of the HSL model system of the collected image (Hue, Saturation and Lightness) were obtained by simple image management (enabled in any computer). The analytical response of the optimised solid-state optical probe against concentration was tested for several mathematical transformations of the colour coordinates. Linear behaviour was observed for logarithm NFX concentration against Hue+Lightness. Under this condition, the sensor exhibited a limit of detection below 50 μM (corresponding to about 16 mg/mL). Visual inspection also enabled semi-quantitative information. The selectivity was ensured against drugs from other chemical groups than fluoroquinolones. Finally, similar procedure was used to prepare an array of sensors for NFX, consisting on different metal species. Cu(II), Mn(II) and aluminon were selected for this purpose. The sensor array was used to detect NFX in aquaculture water, without any prior sample manipulation.