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.

Fractional derivatives: probability interpretation and frequency response of rational approximations

The theory of fractional calculus (FC) is a useful mathematical tool in many applied sciences. Nevertheless, only in the last decades researchers were motivated for the adoption of the FC concepts. There are several reasons for this state of affairs, namely the co-existence of different definitions and interpretations, and the necessity of approximation methods for the real time calculation of fractional derivatives (FDs). In a first part, this paper introduces a probabilistic interpretation of the fractional derivative based on the Grünwald-Letnikov definition. In a second part, the calculation of fractional derivatives through Padé fraction approximations is analyzed. It is observed that the probabilistic interpretation and the frequency response of fraction approximations of FDs reveal a clear correlation between both concepts.

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.

Support System for Rational Use of Electric Energy

This paper presents the system developed to promote the rational use of electric energy among consumers and, thus, increase the energy efficiency. The goal is to provide energy consumers with an application that displays the energy consumption/production profiles, sets up consuming ceilings, defines automatic alerts and alarms, compares anonymously consumers with identical energy usage profiles by region and predicts, in the case of non-residential installations, the expected consumption/production values. The resulting distributed system is organized in two main blocks: front-end and back-end. The front-end includes user interface applications for Android mobile devices and Web browsers. The back-end provides data storage and processing functionalities and is installed in a cloud computing platform - the Google App Engine - which provides a standard Web service interface. This option ensures interoperability, scalability and robustness to the system.

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.

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.

Reformulação de um Sistema de Gestão de Consumos de Energia

Atualmente a energia é considerada um vetor estratégico nas diversas organizações. Assim sendo, a gestão e a utilização racional da energia são consideradas instrumentos fundamentais para a redução dos consumos associados aos processos de produção do sector industrial. As ações de gestão energética não deverão ficar pela fase do projeto das instalações e dos meios de produção, mas sim acompanhar a atividade da Empresa. A gestão da energia deve ser sustentada com base na realização regular de diagnósticos energéticos às instalações consumidoras e concretizada através de planos de atuação e de investimento que apresentem como principal objetivo a promoção da eficiência energética, conduzindo assim à redução dos respetivos consumos e, consequentemente, à redução da fatura energética. Neste contexto, a utilização de ferramentas de apoio à gestão de energia promovem um consumo energético mais racional, ou seja, promovem a eficiência energética e é neste sentido que se insere este trabalho. O presente trabalho foi desenvolvido na Empresa RAR Açúcar e apresentou como principais objetivos: a reformulação do Sistema de Gestão de Consumos de Energia da Empresa, a criação de um modelo quantitativo que permitisse ao Gestor de Energia prever os consumos anuais de água, fuelóleo e eletricidade da Refinaria e a elaboração de um plano de consumos para o ano de 2014 a partir do modelo criado. A reformulação do respetivo Sistema de Gestão de Consumos resultou de um conjunto de etapas. Numa primeira fase foi necessário efetuar uma caraterização e uma análise do atual Sistema de Gestão de Consumos da Empresa, sistema composto por um conjunto de sete ficheiros de cálculo do programa Microsoft Excel©. Terminada a análise, selecionada a informação pertinente e propostas todas as melhorias a introduzir nos ficheiros, procedeu-se à reformulação do respetivo SGE, reduzindo-se o conjunto de ficheiros de cálculo para apenas dois ficheiros, um onde serão efetuados e visualizados todos os registos e outro onde serão realizados os cálculos necessários para o controlo energético da Empresa. O novo Sistema de Gestão de Consumos de Energia será implementado no início do ano de 2015. Relativamente às alterações propostas para as folhas de registos manuais, estas já foram implementadas pela Empresa. Esta aplicação prática mostrou-se bastante eficiente uma vez que permitiu grandes melhorias processuais nomeadamente, menores tempos de preenchimento das mesmas e um encurtamento das rotas efetuadas diariamente pelos operadores. Através do levantamento efetuado aos diversos contadores foi possível identificar todas as áreas onde será necessário a sua instalação e a substituição de todos os contadores avariados, permitindo deste modo uma contabilização mais precisa de todos os consumos da Empresa. Com esta reestruturação o Sistema de Gestão de Consumos tornou-se mais dinâmico, mais claro e, principalmente, mais eficiente. Para a criação do modelo de previsão de consumos da Empresa foi necessário efetuar-se um levantamento dos consumos históricos de água, eletricidade, fuelóleo e produção de açúcar de dois anos. Após este levantamento determinaram-se os consumos específicos de água, fuelóleo e eletricidade diários (para cada semana dos dois anos) e procedeu-se à caracterização destes consumos por tipo de dia. Efetuada a caracterização definiu-se para cada tipo de dia um consumo específico médio com base nos dois anos. O modelo de previsão de consumos foi criado com base nos consumos específicos médios dos dois anos correspondentes a cada tipo de dia. Procedeu-se por fim à verificação do modelo, comparando-se os consumos obtidos através do modelo (consumos previstos) com os consumos reais de cada ano. Para o ano de 2012 o modelo apresenta um desvio de 6% na previsão da água, 12% na previsão da eletricidade e de 6% na previsão do fuelóleo. Em relação ao ano de 2013, o modelo apresenta um erro de 1% para a previsão dos consumos de água, 8% para o fuelóleo e de 1% para a eletricidade. Este modelo permitirá efetuar contratos de aquisição de energia elétrica com maior rigor o que conduzirá a vantagens na sua negociação e consequentemente numa redução dos custos resultantes da aquisição da mesma. Permitirá também uma adequação dos fluxos de tesouraria à necessidade reais da Empresa, resultante de um modelo de previsão mais rigoroso e que se traduz numa mais-valia financeira para a mesma. Foi também proposto a elaboração de um plano de consumos para o ano de 2014 a partir do modelo criado em função da produção prevista para esse mesmo ano. O modelo apresenta um desvio de 24% na previsão da água, 0% na previsão da eletricidade e de 28% na previsão do fuelóleo.

Despacho Económico de um SEE com coordenação Hidrotérmica Departamento de Engenharia Electrotécnica

O Despacho económico de um sistema eléctrico de energia com a coordenação hidrotérmica tem como objectivo alcançar a operação óptima do sistema em um determinado período de tempo, ao menor custo possível, e com alto grau de fiabilidade. O problema é muito complexo, pois depende do grau de dificuldade em se prever os caudais dos afluentes, e da capacidade das albufeiras das centrais hídricas. De um modo geral, a produção térmica é determinada de modo a proporcionar o uso mais racional possível da água, dentro do contexto de incertezas quanto às afluências futuras, de modo a, por um lado manter o sistemas o mais económico possível, e por outro, evitar o desperdício energético implícito em descarregamentos de volumes de água turbináveis. Neste trabalho é proposta uma metodologia baseada em programação linear para a solução da coordenação hidrotérmica de curto prazo, e que permite obter custos-sombra de água em centrais hídricas com armazenamento. Esta metodologia foi posteriormente implementado num programa computacional em Microsoft Excel 2010 para a solução numa primeira fase, da rede de 24 barramentos do IEEE, e numa segunda fase, para a solução da Rede Nacional de Transporte referente ao ano de 2010. Para efeitos de análise e validação de dados, os dados provenientes do programa, são depois comparados aos dados dos relatórios da REN. Por último, os dados provenientes do programa em Excel são colocados e analisados no programa PowerWorld Simulator 8.0.

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.

Solid contact PVC membrane electrodes based on neutral or charged carriers for the selective reading of anionic sulfamethoxazole and their application to the analysis of aquaculture water

Sulfamethoxazole (SMX) is among the antibiotics employed in aquaculture for prophylactic and therapeutic reasons. Environmental and food spread may be prevented by controlling its levels in several stages of fish farming. The present work proposes for this purpose new SMX selective electrodes for the potentiometric determination of this sulphonamide in water. The selective membranes were made of polyvinyl chloride (PVC) with tetraphenylporphyrin manganese (III) chloride or cyclodextrin-based acting as ionophores. 2-nitrophenyl octyl ether was employed as plasticizer and tetraoctylammonium, dimethyldioctadecylammonium bromide or potassium tetrakis (4-chlorophenyl) borate was used as anionic or cationic additive. The best analytical performance was reported for ISEs of tetraphenylporphyrin manganese (III) chloride with 50% mol of potassium tetrakis (4-chlorophenyl) borate compared to ionophore. Nersntian behaviour was observed from 4.0 × 10−5 to 1.0 × 10−2 mol/L (10.0 to 2500 µg/mL), and the limit of detection was 1.2 × 10−5 mol/L (3.0 µg/mL). In general, the electrodes displayed steady potentials in the pH range of 6 to 9. Emf equilibrium was reached before 15 s in all concentration levels. The electrodes revealed good discriminating ability in environmental samples. The analytical application to contaminated waters showed recoveries from 96 to 106%.

Microcystin-LR detection in water by the Fabry–Pérot interferometer using an optical fibre coated with a sol–gel imprinted sensing membrane

Cyanobacteria deteriorate the water quality and are responsible for emerging outbreaks and epidemics causing harmful diseases in Humans and animals because of their toxins. Microcystin-LR (MCT) is one of the most relevant cyanotoxin, being the most widely studied hepatotoxin. For safety purposes, the World Health Organization recommends a maximum value of 1 μg L−1 of MCT in drinking water. Therefore, there is a great demand for remote and real-time sensing techniques to detect and quantify MCT. In this work a Fabry–Pérot sensing probe based on an optical fibre tip coated with a MCT selective thin film is presented. The membranes were developed by imprinting MCT in a sol–gel matrix that was applied over the tip of the fibre by dip coating. The imprinting effect was obtained by curing the sol–gel membrane, prepared with (3-aminopropyl) trimethoxysilane (APTMS), diphenyl-dimethoxysilane (DPDMS), tetraethoxysilane (TEOS), in the presence of MCT. The imprinting effect was tested by preparing a similar membrane without template. In general, the fibre Fabry–Pérot with a Molecular Imprinted Polymer (MIP) sensor showed low thermal effect, thus avoiding the need of temperature control in field applications. It presented a linear response to MCT concentration within 0.3–1.4 μg L−1 with a sensitivity of −12.4 ± 0.7 nm L μg−1. The corresponding Non-Imprinted Polymer (NIP) displayed linear behaviour for the same MCT concentration range, but with much less sensitivity, of −5.9 ± 0.2 nm L μg−1. The method shows excellent selectivity for MCT against other species co-existing with the analyte in environmental waters. It was successfully applied to the determination of MCT in contaminated samples. The main advantages of the proposed optical sensor include high sensitivity and specificity, low-cost, robustness, easy preparation and preservation.

Exposure of Lycopersicon Esculentum to Microcystin-LR: Effects in the Leaf Proteome and Toxin Translocation from Water to Leaves and Fruits

Natural toxins such as those produced by freshwater cyanobacteria have been regarded as an emergent environmental threat. However, the impact of these water contaminants in agriculture is not yet fully understood. The aim of this work was to investigate microcystin-LR (MC-LR) toxicity in Lycopersicon esculentum and the toxin accumulation in this horticultural crop. Adult plants (2 month-old) grown in a greenhouse environment were exposed for 2 weeks to either pure MC-LR (100 μg/L) or Microcystis aeruginosa crude extracts containing 100 μg/L MC-LR. Chlorophyll fluorescence was measured, leaf proteome investigated with two-dimensional gel electrophoresis and Matrix Assisted Laser Desorption Ionization Time-of-Flight (MALDI-TOF)/TOF, and toxin bioaccumulation assessed by liquid chromatography-mass spectrometry (LC-MS)/MS. Variations in several protein markers (ATP synthase subunits, Cytochrome b6-f complex iron-sulfur, oxygen-evolving enhancer proteins) highlight the decrease of the capacity of plants to synthesize ATP and to perform photosynthesis, whereas variations in other proteins (ribulose-1,5-bisphosphate carboxylase/oxygenase large subunit and ribose-5-phosphate isomerase) suggest an increase of carbon fixation and decrease of carbohydrate metabolism reactions in plants exposed to pure MC-LR and cyanobacterial extracts, respectively. MC-LR was found in roots (1635.21 μg/kg fw), green tomatoes (5.15–5.41 μg/kg fw), mature tomatoes (10.52–10.83 μg/kg fw), and leaves (12,298.18 μg/kg fw). The results raise concerns relative to food safety and point to the necessity of monitoring the bioaccumulation of water toxins in agricultural systems affected by cyanotoxin contamination.