Interlaboratory validation of an environmental monitoring method for trace analysis of endocrine disrupting compounds

Environmental pollution continues to be an emerging study field, as there are thousands of anthropogenic compounds mixed in the environment whose possible mechanisms of toxicity and physiological outcomes are of great concern. Developing methods to access and prioritize the screening of these compounds at trace levels in order to support regulatory efforts is, therefore, very important. A methodology based on solid phase extraction followed by derivatization and gas chromatography-mass spectrometry analysis was developed for the assessment of four endocrine disrupting compounds (EDCs) in water matrices: bisphenol A, estrone, 17b-estradiol and 17a-ethinylestradiol. The study was performed, simultaneously, by two different laboratories in order to evaluate the robustness of the method and to increase the quality control over its application in routine analysis. Validation was done according to the International Conference on Harmonisation recommendations and other international guidelines with specifications for the GC-MS methodology. Matrix-induced chromatographic response enhancement was avoided by using matrix-standard calibration solutions and heteroscedasticity has been overtaken by a weighted least squares linear regression model application. Consistent evaluation of key analytical parameters such as extraction efficiency, sensitivity, specificity, linearity, limits of detection and quantification, precision, accuracy and robustness was done in accordance with standards established for acceptance. Finally, the application of the optimized method in the assessment of the selected analytes in environmental samples suggested that it is an expedite methodology for routine analysis of EDC residues in water matrices.

Development of a simple analytical method for the simultaneousdetermination of paracetamol, paracetamol-glucuronide andp-aminophenol in river water

Paracetamol is among the most worldwide consumed pharmaceuticals. Although its occurrence in the environment is well documented, data about the presence of its metabolites and transformation products is very scarce. The present work describes the development of an analytical method for the simultaneous determination of paracetamol, its principal metabolite (paracetamol-glucuronide) and its main transformation product (p-aminophenol) based on solid phase extraction (SPE) and high performance liquid chromatography coupled to diode array detection (HPLC-DAD). The method was applied to analysis of river waters, showing to be suitable to be used in routine analysis. Different SPE sorbents were compared and the use of two Oasis WAX cartridges in tandem proved to be the most adequate approach for sample clean up and pre-concentration. Under optimized conditions, limits of detection in the range 40–67 ng/L were obtained, as well as mean recoveries between 60 and 110% with relative standard deviations (RSD) below 6%. Finally, the developed SPE-HPLC/DAD method was successfully applied to the analysis of the selected compounds in samples from seven rivers located in the north of Portugal. Nevertheless all the compounds were detected, it was the first time that paracetamol-glucuronide was found in river water at concentrations up to 3.57 μg/L.

Enantiomeric fraction evaluation of pharmaceuticals in environmentalmatrices by liquid chromatography-tandem mass spectrometry

The interest for environmental fate assessment of chiral pharmaceuticals is increasing and enantioselective analytical methods are mandatory. This study presents an enantioselective analytical method for the quantification of seven pairs of enantiomers of pharmaceuticals and a pair of a metabolite. The selected chiral pharmaceuticals belong to three different therapeutic classes, namely selective serotonin reuptake inhibitors (venlafaxine, fluoxetine and its metabolite norfluoxetine), beta-blockers (alprenolol, bisoprolol, metoprolol, propranolol) and a beta2-adrenergic agonist (salbutamol). The analytical method was based on solid phase extraction followed by liquid chromatography tandem mass spectrometry with a triple quadrupole analyser. Briefly, Oasis® MCX cartridges were used to preconcentrate 250 mL of water samples and the reconstituted extracts were analysed with a Chirobiotic™ V under reversed mode. The effluent of a laboratory-scale aerobic granular sludge sequencing batch reactor (AGS-SBR) was used to validate the method. Linearity (r2 > 0.99), selectivity and sensitivity were achieved in the range of 20–400 ng L−1 for all enantiomers, except for norfluoxetine enantiomers which range covered 30–400 ng L−1. The method detection limits were between 0.65 and 11.5 ng L−1 and the method quantification limits were between 1.98 and 19.7 ng L−1. The identity of all enantiomers was confirmed using two MS/MS transitions and its ion ratios, according to European Commission Decision 2002/657/EC. This method was successfully applied to evaluate effluents of wastewater treatment plants (WWTP) in Portugal. Venlafaxine and fluoxetine were quantified as non-racemic mixtures (enantiomeric fraction ≠ 0.5). The enantioselective validated method was able to monitor chiral pharmaceuticals in WWTP effluents and has potential to assess the enantioselective biodegradation in bioreactors. Further application in environmental matrices as surface and estuarine waters can be exploited.

Oxidative Leaching of metals from electronic waste with solutions based on quaternary ammonium salts

The treatment of electric and electronic waste (WEEE) is a problem which receives ever more attention. An inadequate treatment results in harmful products ending up in the environment. This project intends to investigate the possibilities of an alternative route for recycling of metals from printed circuit boards (PCBs) obtained from rejected computers. The process is based on aqueous solutions composed of an etchant, either 0.2 M CuCl2.2H2O or 0.2 M FeCl3.6H2O, and a quaternary ammonium salt (quat) such as choline chloride or chlormequat. These solutions are reminiscent of deep eutectic solvents (DES) based on quats. DES are quite similar to ionic liquids (ILs) and are used as well as alternative solvents with a great diversity of physical properties, making them attractive for replacement of hazardous, volatile solvents (e.g. VOCs). A remarkable difference between genuine DES and ILs with the solutions used in this project is the addition of rather large quantities of water. It is shown the presence of water has a lot of advantages on the leaching of metals, while the properties typical for DES still remain. The oxidizing capacities of Cu(II) stem from the existence of a stable Cu(I) component in quat based DES and thus the leaching stems from the activity of the Cu(II)/Cu(I) redox couple. The advantage of Fe(III) in combination with DES is the fact that the Fe(III)/Fe(II) redox couple becomes reversible, which is not true in pure water. This opens perspectives for regeneration of the etching solution. In this project the leaching of copper was studied as a function of gradual increasing water content from 0 - 100w% with the same concentration of copper chloride or iron(III) chloride at room temperature and 80ºC. The solutions were also tested on real PCBs. At room temperature a maximum leaching effect for copper was obtained with 30w% choline chloride with 0.2 M CuCl2.2H2O. The leaching effect is still stronger at 80°C, b ut of course these solutions are more energy consuming. For aluminium, tin, zinc and lead, the leaching was faster at 80ºC. Iron and nickel dissolved easily at room temperature. The solutions were not able to dissolve gold, silver, rhodium and platinum.

Hand gesture recognition system based in computer vision and machine learning : applications on human-machine interaction

Sendo uma forma natural de interação homem-máquina, o reconhecimento de gestos implica uma forte componente de investigação em áreas como a visão por computador e a aprendizagem computacional. O reconhecimento gestual é uma área com aplicações muito diversas, fornecendo aos utilizadores uma forma mais natural e mais simples de comunicar com sistemas baseados em computador, sem a necessidade de utilização de dispositivos extras. Assim, o objectivo principal da investigação na área de reconhecimento de gestos aplicada à interacção homemmáquina é o da criação de sistemas, que possam identificar gestos específicos e usálos para transmitir informações ou para controlar dispositivos. Para isso as interfaces baseados em visão para o reconhecimento de gestos, necessitam de detectar a mão de forma rápida e robusta e de serem capazes de efetuar o reconhecimento de gestos em tempo real. Hoje em dia, os sistemas de reconhecimento de gestos baseados em visão são capazes de trabalhar com soluções específicas, construídos para resolver um determinado problema e configurados para trabalhar de uma forma particular. Este projeto de investigação estudou e implementou soluções, suficientemente genéricas, com o recurso a algoritmos de aprendizagem computacional, permitindo a sua aplicação num conjunto alargado de sistemas de interface homem-máquina, para reconhecimento de gestos em tempo real. A solução proposta, Gesture Learning Module Architecture (GeLMA), permite de forma simples definir um conjunto de comandos que pode ser baseado em gestos estáticos e dinâmicos e que pode ser facilmente integrado e configurado para ser utilizado numa série de aplicações. É um sistema de baixo custo e fácil de treinar e usar, e uma vez que é construído unicamente com bibliotecas de código. As experiências realizadas permitiram mostrar que o sistema atingiu uma precisão de 99,2% em termos de reconhecimento de gestos estáticos e uma precisão média de 93,7% em termos de reconhecimento de gestos dinâmicos. Para validar a solução proposta, foram implementados dois sistemas completos. O primeiro é um sistema em tempo real capaz de ajudar um árbitro a arbitrar um jogo de futebol robótico. A solução proposta combina um sistema de reconhecimento de gestos baseada em visão com a definição de uma linguagem formal, o CommLang Referee, à qual demos a designação de Referee Command Language Interface System (ReCLIS). O sistema identifica os comandos baseados num conjunto de gestos estáticos e dinâmicos executados pelo árbitro, sendo este posteriormente enviado para um interface de computador que transmite a respectiva informação para os robôs. O segundo é um sistema em tempo real capaz de interpretar um subconjunto da Linguagem Gestual Portuguesa. As experiências demonstraram que o sistema foi capaz de reconhecer as vogais em tempo real de forma fiável. Embora a solução implementada apenas tenha sido treinada para reconhecer as cinco vogais, o sistema é facilmente extensível para reconhecer o resto do alfabeto. As experiências também permitiram mostrar que a base dos sistemas de interação baseados em visão pode ser a mesma para todas as aplicações e, deste modo facilitar a sua implementação. A solução proposta tem ainda a vantagem de ser suficientemente genérica e uma base sólida para o desenvolvimento de sistemas baseados em reconhecimento gestual que podem ser facilmente integrados com qualquer aplicação de interface homem-máquina. A linguagem formal de definição da interface pode ser redefinida e o sistema pode ser facilmente configurado e treinado com um conjunto de gestos diferentes de forma a serem integrados na solução final.

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%.

Self-optimization module for scheduling using case-based reasoning

Metaheuristics performance is highly dependent of the respective parameters which need to be tuned. Parameter tuning may allow a larger flexibility and robustness but requires a careful initialization. The process of defining which parameters setting should be used is not obvious. The values for parameters depend mainly on the problem, the instance to be solved, the search time available to spend in solving the problem, and the required quality of solution. This paper presents a learning module proposal for an autonomous parameterization of Metaheuristics, integrated on a Multi-Agent System for the resolution of Dynamic Scheduling problems. The proposed learning module is inspired on Autonomic Computing Self-Optimization concept, defining that systems must continuously and proactively improve their performance. For the learning implementation it is used Case-based Reasoning, which uses previous similar data to solve new cases. In the use of Case-based Reasoning it is assumed that similar cases have similar solutions. After a literature review on topics used, both AutoDynAgents system and Self-Optimization module are described. Finally, a computational study is presented where the proposed module is evaluated, obtained results are compared with previous ones, some conclusions are reached, and some future work is referred. It is expected that this proposal can be a great contribution for the self-parameterization of Metaheuristics and for the resolution of scheduling problems on dynamic environments.

Cooperative scheduling system with emergent swarm based behavior

This paper presents a Swarm based Cooperation Mechanism for scheduling optimization. We intend to conceptualize real manufacturing systems as interacting autonomous entities in order to support decision making in agile manufacturing environments. Agents coordinate their actions automatically without human supervision considering a common objective – global scheduling solution taking advantages from collective behavior of species through implicit and explicit cooperation. The performance of the cooperation mechanism will be evaluated consider implicit cooperation at first stage through ACS, PSO and ABC algorithms and explicit through cooperation mechanism application.

Transmission costs allocation based on optimal re-dispatch

Congestion management of transmission power systems has achieve high relevance in competitive environments, which require an adequate approach both in technical and economic terms. This paper proposes a new methodology for congestion management and transmission tariff determination in deregulated electricity markets. The congestion management methodology is based on a reformulated optimal power flow, whose main goal is to obtain a feasible solution for the re-dispatch minimizing the changes in the transactions resulting from market operation. The proposed transmission tariffs consider the physical impact caused by each market agents in the transmission network. The final tariff considers existing system costs and also costs due to the initial congestion situation and losses. This paper includes a case study for the 118 bus IEEE test case.

Development of novel ionic liquids based on ampicillin

Novel ionic liquids containing ampicillin as an active pharmaceutical ingredient anion were prepared with good yields by using a new, efficient synthetic procedure based on the neutralization of a moderately basic ammonia solution of ampicillin with different organic cation hydroxides. The relevant physical and thermal properties of these novel ionic liquids based on ampicillin were also evaluated.

Optimal methodology for distribution systems reconfiguration based on OPF and solved by decomposition technique

This paper presents a new and efficient methodology for distribution network reconfiguration integrated with optimal power flow (OPF) based on a Benders decomposition approach. The objective minimizes power losses, balancing load among feeders and subject to constraints: capacity limit of branches, minimum and maximum power limits of substations or distributed generators, minimum deviation of bus voltages and radial optimal operation of networks. The Generalized Benders decomposition algorithm is applied to solve the problem. The formulation can be embedded under two stages; the first one is the Master problem and is formulated as a mixed integer non-linear programming problem. This stage determines the radial topology of the distribution network. The second stage is the Slave problem and is formulated as a non-linear programming problem. This stage is used to determine the feasibility of the Master problem solution by means of an OPF and provides information to formulate the linear Benders cuts that connect both problems. The model is programmed in GAMS. The effectiveness of the proposal is demonstrated through two examples extracted from the literature.

Context-aware emotion-based model for group decision making

Involving groups in important management processes such as decision making has several advantages. By discussing and combining ideas, counter ideas, critical opinions, identified constraints, and alternatives, a group of individuals can test potentially better solutions, sometimes in the form of new products, services, and plans. In the past few decades, operations research, AI, and computer science have had tremendous success creating software systems that can achieve optimal solutions, even for complex problems. The only drawback is that people don’t always agree with these solutions. Sometimes this dissatisfaction is due to an incorrect parameterization of the problem. Nevertheless, the reasons people don’t like a solution might not be quantifiable, because those reasons are often based on aspects such as emotion, mood, and personality. At the same time, monolithic individual decisionsupport systems centered on optimizing solutions are being replaced by collaborative systems and group decision-support systems (GDSSs) that focus more on establishing connections between people in organizations. These systems follow a kind of social paradigm. Combining both optimization- and socialcentered approaches is a topic of current research. However, even if such a hybrid approach can be developed, it will still miss an essential point: the emotional nature of group participants in decision-making tasks. We’ve developed a context-aware emotion based model to design intelligent agents for group decision-making processes. To evaluate this model, we’ve incorporated it in an agent-based simulator called ABS4GD (Agent-Based Simulation for Group Decision), which we developed. This multiagent simulator considers emotion- and argument based factors while supporting group decision-making processes. Experiments show that agents endowed with emotional awareness achieve agreements more quickly than those without such awareness. Hence, participant agents that integrate emotional factors in their judgments can be more successful because, in exchanging arguments with other agents, they consider the emotional nature of group decision making.

Estudo de optimização energética da unidade 1400

O estudo de optimização energética da Unidade 1400 da Fábrica de Combustíveis da Refinaria de Matosinhos da Galp Energia foi realizado com base no projecto de revamping elaborado pela AXENS, devido à existência de dúvidas (Galp Energia) de que aquele projecto não estivesse, do ponto de vista energético, totalmente rentabilizado. Para a consecução deste estudo, foi aplicado o conceito Pinch (Ponto de Estrangulamento), recorrendo-se quer a software dedicado disponível (ASPEN Energy Analyser), quer ao cálculo da Cascata de Calor. Os resultados obtidos em definitivo foram-no através deste último, tendo servido o primeiro apenas como indicador, devido à existência de incoerências (pelo menos aparentes). Foram considerados três cenários, tendo apenas como elemento diferenciador o valor de ΔTmin: 10, 15 e 20 oC. Foi detectado, somente para este último (20 oC), um ponto de estrangulamento. Os três cenários concordam na necessidade de inclusão de um novo permutador de calor entre a corrente de gasóleo após sofrer reacção de hidrogenação (fundo do reactor) e após dois estágios de arrefecimento e a corrente de gasóleo à entrada da Unidade e após recepção do reciclo de hidrogénio, constituindo assim a sua fonte inicial de aquecimento. Como consequência, também são reduzidas as necessidades de serviço da fornalha pré-reactor e das utilidades de arrefecimento. Para o cálculo do novo permutador de calor, seguiram-se duas vias: carcaça e tubos convencional e carcaça e tubos com disposição helicoidal das chicanas (Helixchanger®). Para o primeiro tipo, recorreu-se ao software ASPEN Exchanger Design & Rating, sendo, para o segundo, a empresa detentora da tecnologia (Lummus Technology) a fornecer a solução pretendida. Procedeu-se a um breve estudo de rentabilidade económica do investimento em causa, considerando o seu maior valor (Helixchanger®), sendo o resultado favorável à sua aplicação.

Desenvolvimento de um sensor óptico para determinação de Norfloxacina

A presente dissertação descreve o desenvolvimento e a caracterização de sensores ópticos com base em membranas de poli(cloreto de vinilo), PVC, para determinação de Norfloxacina em amostras do sector da aquacultura. Estes sensores basearam-se na reacção colorimétrica entre um metal imobilizado em PVC e a Norfloxacina. O metal foi escolhido com base em ensaios prévios de reacção colorimétrica entre a Norfloxacina e várias espécies metálicas, nomeadamente, Fe(III), Al(III), Pb(II), Aluminon, Mo(II), Mn(II), Ni(II), Cu(II), Co(II), Sn(II) e V(V). A reacção mais intensa foi obtida com o Fe(III). Neste sentido, numa primeira fase foram desenvolvidos sensores baseados em Fe(III). O efeito de alguns parâmetros experimentais na resposta desses sensores foi avaliado de modo univariado. Incluem-se aqui o efeito do pH, avaliado entre 2,00 e 6,00, e o da concentração de Fe(III), variada entre cerca de 1,00x10-5 M e 2,00x10-4 M. Os melhores valores foram obtidos a pH 3, para o qual se verificou um comportamento linear entre cerca de 1,00x10-5 M e 1,70x10-4 M de Fe(III). Utilizando as condições seleccionadas anteriormente, procedeu-se à caracterização do complexo sob ponto de vista químico. Os valores obtidos apontaram para a necessidade de um excesso de Fe(III) de, pelo menos, 10 vezes, no sentido de garantir a máxima extensão de complexação. O complexo referido apresentou, nestas condições, um comportamento linear ao longo do intervalo de concentrações de cerca de 7,00x10-5 M a 7,00x10-4 M em NOR. O complexo formado foi estável ao longo de 90 minutos. As condições óptimas para análise desse complexo numa superfície sólida foram obtidas após avaliação do efeito da quantidade de Fe(III) e do tipo e quantidade de solvente mediador (o-nitrofenil octil éter, di-n-octilftalato, dibutilftalato, bis(etilhexil)sebacato, bis(etilhexil)ftalato). O bis(etilhexil)sebacato foi o solvente mediador escolhido e a relação de quantidade entre o PVC e o solvente mediador foi igual a 1:2. O procedimento de preparação do sensor sólido e subsequente optimização foi aplicado a outras espécies metálicas, para além do Fe(III), tais como, Cu(II), Mn(II) e aluminon. A conjugação de todos estes metais permitiu desenvolver um array de sensores para despistagem de Norfloxacina em águas de aquacultura. Algumas membranas sensoras foram aplicadas com sucesso no controlo de Norfloxacina em amostras de águas ambientais dopadas. Os resultados obtidos com membranas de Fe(III) e Cu(II) foram exactos, tendo-se registado valores de concentração próximos dos reais. O método proposto permitiu, por isso, a despistagem rápida e eficaz da presença de um antibiótico em águas ambientais, permitindo ainda o seu doseamento a um baixo custo. Numa perspectiva de rotina, e tendo em vista a despistagem deste antibiótico, este método revelou-se mais rápido e mais barato do que os demais métodos descritos na literatura para este efeito.