Analysis of polycyclic aromatic hydrocarbons in fish: evaluation of a quick, easy, cheap, effective, rugged, and safe extraction method

QuEChERS method was evaluated for extraction of 16 PAHs from fish samples. For a selective measurement of the compounds, extracts were analysed by LC with fluorescence detection. The overall analytical procedure was validated by systematic recovery experiments at three levels and by using the standard reference material SRM 2977 (mussel tissue). The targeted contaminants, except naphthalene and acenaphthene, were successfully extracted from SRM 2977 with recoveries ranging from 63.5–110.0% with variation coefficients not exceeding 8%. The optimum QuEChERS conditions were the following: 5 g of homogenised fish sample, 10 mL of ACN, agitation performed by vortex during 3 min. Quantification limits ranging from 0.12– 1.90 ng/g wet weight (0.30–4.70 µg/L) were obtained. The optimized methodology was applied to assess the safety concerning PAHs contents of horse mackerel (Trachurus trachurus), chub mackerel (Scomber japonicus), sardine (Sardina pilchardus) and farmed seabass (Dicentrarchus labrax). Although benzo(a)pyrene, the marker used for evaluating the carcinogenic risk of PAHs in food, was not detected in the analysed samples (89 individuals corresponding to 27 homogenized samples), the overall mean concentration ranged from 2.52 l 1.20 ng/g in horse mackerel to 14.6 ± 2.8 ng/ g in farmed seabass. Significant differences were found between the mean PAHs concentrations of the four groups.

Detection of ZnS phases in CZTS thin-films by EXAFS

Copper zinc tin sulfide (CZTS) is a promising Earthabundant thin-film solar cell material; it has an appropriate band gap of ~1.45 eV and a high absorption coefficient. The most efficient CZTS cells tend to be slightly Zn-rich and Cu-poor. However, growing Zn-rich CZTS films can sometimes result in phase decomposition of CZTS into ZnS and Cu2SnS3, which is generally deleterious to solar cell performance. Cubic ZnS is difficult to detect by XRD, due to a similar diffraction pattern. We hypothesize that synchrotron-based extended X-ray absorption fine structure (EXAFS), which is sensitive to local chemical environment, may be able to determine the quantity of ZnS phase in CZTS films by detecting differences in the second-nearest neighbor shell of the Zn atoms. Films of varying stoichiometries, from Zn-rich to Cu-rich (Zn-poor) were examined using the EXAFS technique. Differences in the spectra as a function of Cu/Zn ratio are detected. Linear combination analysis suggests increasing ZnS signal as the CZTS films become more Zn-rich. We demonstrate that the sensitive technique of EXAFS could be used to quantify the amount of ZnS present and provide a guide to crystal growth of highly phase pure films.

Personality, emotion, and mood in agent-based group decision making

Group decision making plays an important role in organizations, especially in the present-day economy that demands high-quality, yet quick decisions. Group decision-support systems (GDSSs) are interactive computer-based environments that support concerted, coordinated team efforts toward the completion of joint tasks. The need for collaborative work in organizations has led to the development of a set of general collaborative computer-supported technologies and specific GDSSs that support distributed groups (in time and space) in various domains. However, each person is unique and has different reactions to various arguments. Many times a disagreement arises because of the way we began arguing, not because of the content itself. Nevertheless, emotion, mood, and personality factors have not yet been addressed in GDSSs, despite how strongly they influence results. Our group’s previous work considered the roles that emotion and mood play in decision making. In this article, we reformulate these factors and include personality as well. Thus, this work incorporates personality, emotion, and mood in the negotiation process of an argumentbased group decision-making process. Our main goal in this work is to improve the negotiation process through argumentation using the affective characteristics of the involved participants. Each participant agent represents a group decision member. This representation lets us simulate people with different personalities. The discussion process between group members (agents) is made through the exchange of persuasive arguments. Although our multiagent architecture model4 includes two types of agents—the facilitator and the participant— this article focuses on the emotional, personality, and argumentation components of the participant agent.

Analysing organochlorine pesticides in strawberry jams using GC-ECD, GC-MS/MS and QuEChERS sample preparation

This paper describes a comparison of adaptations of the QuEChERS (quick, easy, cheap, effective, rugged and safe) approach for the determination of 14 organochlorine pesticide (OCP) residues in strawberry jam by concurrent use of gas chromatography (GC) coupled to electron capture detector (ECD) and GC tandem mass spectrometry (GC-MS/MS). Three versions were tested based on the original QuEChERS method. The results were good (overall average of 89% recoveries with 15% RSD) using the ultrasonic bath at five spiked levels. Performance characteristics, such as accuracy, precision, linear range, limits of detection (LOD) and quantification (LOQ), were determined for each pesticide. LOD ranged from 0.8 to 8.9 microg kg-1 ; LOQ was in the range of 2.5–29.8 microg kg- 1; and calibration curves were linear (r2>0.9970) in the whole range of the explored concentrations (5–100 microg kg- 1). The LODs of these pesticides were much lower than the maximum residue levels (MRLs) allowed in Europe for strawberries. The method was successfully applied to the quantification of OCP in commercially available jams. The OCPs were detected lower than the LOD.

Plataforma remota de gestão de um parque de GateBoxes

A monitorização de redes é um aspeto de elevada importância, principalmente em redes de média ou grande dimensão. A necessidade de utilização de uma ferramenta para realização dessa gestão facilita o trabalho e proporciona de uma forma mais rápida e eficaz a identificação de problemas na rede e nos seus sistemas. Neste sentido, o presente trabalho tem como objetivo o desenvolvimento de uma solução para a monitorização de GateBoxes, um dos produtos desenvolvidos e comercializados pela empresa NextToYou. A necessidade de monitorização das GateBoxes, por parte da NextToYou, é essencial para que possa detetar falhas no seu funcionamento ou realizar notificações aquando da deteção de problemas para uma rápida resolução. Neste contexto a empresa decidiu implementar uma ferramenta para a referida monitorização e propôs, no âmbito da tese, o desenvolvimento de uma aplicação que satisfizesse esses propósitos. Disponibilizou então, para o desenvolvimento uma plataforma, a WebForge, e definiu alguns requisitos funcionais dessa ferramenta, tais como, a monitorização remota de informação, gestão de alarmes, geração de avisos e notificações. Para a elaboração deste trabalho foram realizados estudos teóricos sobre o tema da gestão e monitorização remotas, realizando-se posteriormente o desenvolvimento de uma aplicação para a monitorização de GateBoxes. Após a implementação efetuou-se a validação do trabalho realizado através da execução de testes e demonstrações, de forma a poder validar e verificar o desempenho do sistema.

Determination of pesticides in fruit and fruit juices by chromatographic methods. An overview

In order to combat a variety of pests, pesticides are widely used in fruits. Several extraction procedures (liquid extraction, single drop microextraction, microwave-assisted extraction, pressurized liquid extraction, supercritical fluid extraction, solid-phase extraction, solid-phase microextraction, matrix solid-phase dispersion, and stir bar sorptive extraction) have been reported to determine pesticide residues in fruits and fruit juices. The significant change in recent years is the introduction of the Quick, Easy, Cheap, Effective, Rugged, and Safe (QuEChERS) methods in these matrices analysis. A combination of techniques reported the use of new extraction methods and chromatography to provide better quantitative recoveries at low levels. The use of mass spectrometric detectors in combination with liquid and gas chromatography has played a vital role to solve many problems related to food safety. The main attention in this review is on the achievements that have been possible because of the progress in extraction methods and the latest advances and novelties in mass spectrometry, and how these progresses have influenced the best control of food, allowing for an increase in the food safety and quality standards.

Real time manufacturing systems simulator

A área da simulação computacional teve um rápido crescimento desde o seu apareciment, sendo actualmente uma das ciências de gestão e de investigação operacional mais utilizadas. O seu princípio baseia-se na replicação da operação de processos ou sistemas ao longo de períodos de tempo, tornando-se assim uma metodologia indispensável para a resolução de variados problemas do mundo real, independentemente da sua complexidade. Das inúmeras áreas de aplicação, nos mais diversos campos, a que mais se destaca é a utilização em sistemas de produção, onde o leque de aplicações disponível é muito vasto. A sua aplicação tem vindo a ser utilizada para solucionar problemas em sistemas de produção, uma vez que permite às empresas ajustar e planear de uma maneira rápida, eficaz e ponderada as suas operações e os seus sistemas, permitindo assim uma rápida adaptação das mesmas às constantes mudanças das necessidades da economia global. As aplicações e packages de simulação têm seguindo as tendências tecnológicas pelo que é notório o recurso a tecnologias orientadas a objectos para o desenvolvimento das mesmas. Este estudo baseou-se, numa primeira fase, na recolha de informação de suporte aos conceitos de modelação e simulação, bem como a respectiva aplicação a sistemas de produção em tempo real. Posteriormente centralizou-se no desenvolvimento de um protótipo de uma aplicação de simulação de ambientes de fabrico em tempo real. O desenvolvimento desta ferramenta teve em vista eventuais fins pedagógicos e uma utilização a nível académico, sendo esta capaz de simular um modelo de um sistema de produção, estando também dotada de animação. Sem deixar de parte a possibilidade de integração de outros módulos ou, até mesmo, em outras plataformas, houve ainda a preocupação acrescida de que a sua implementação recorresse a metodologias de desenvolvimento orientadas a objectos.

Analysis of pesticide residues in strawberries and soils by GC-MS/MS, LC-MS/MS and two-dimensional GC-timeof- flight MS comparing organic and integrated pest management farming

This study analysed 22 strawberry and soil samples after their collection over the course of 2 years to compare the residue profiles from organic farming with integrated pest management practices in Portugal. For sample preparation, we used the citrate-buffered version of the quick, easy, cheap, effective, rugged, and safe (QuEChERS) method. We applied three different methods for analysis: (1) 27 pesticides were targeted using LC-MS/MS; (2) 143 were targeted using low pressure GC-tandem mass spectrometry (LP-GC-MS/MS); and (3) more than 600 pesticides were screened in a targeted and untargeted approach using comprehensive, two-dimensional gas chromatography time-of-flight mass spectrometry (GC × GC-TOF-MS). Comparison was made of the analyses using the different methods for the shared samples. The results were similar, thereby providing satisfactory confirmation of both similarly positive and negative findings. No pesticides were found in the organic-farmed samples. In samples from integrated pest management practices, nine pesticides were determined and confirmed to be present, ranging from 2 μg kg−1 for fluazifop-pbutyl to 50 μg kg−1 for fenpropathrin. Concentrations of residues in strawberries were less than European maximum residue limits.

Multiple Linear Regression and Artificial Neural Networks to Predict Time and Efficiency of Soil Vapor Extraction

The prediction of the time and the efficiency of the remediation of contaminated soils using soil vapor extraction remain a difficult challenge to the scientific community and consultants. This work reports the development of multiple linear regression and artificial neural network models to predict the remediation time and efficiency of soil vapor extractions performed in soils contaminated separately with benzene, toluene, ethylbenzene, xylene, trichloroethylene, and perchloroethylene. The results demonstrated that the artificial neural network approach presents better performances when compared with multiple linear regression models. The artificial neural network model allowed an accurate prediction of remediation time and efficiency based on only soil and pollutants characteristics, and consequently allowing a simple and quick previous evaluation of the process viability.

Comparison of Disposable Pipette Extraction and Dispersive Solid-Phase Extraction in the QuEChERS Method for Analysis of Pesticides in Strawberries

In this study, we sought to assess the applicability of GC–MS/MS for the identification and quantification of 36 pesticides in strawberry from integrated pest management (IPM) and organic farming (OF). Citrate versions of QuEChERS (quick, easy, cheap, effective, rugged and safe) using dispersive solid-phase extraction (d-SPE) and disposable pipette extraction (DPX) for cleanup were compared for pesticide extraction. For cleanup, a combination of MgSO4, primary secondary amine and C18 was used for both the versions. Significant differences were observed in recovery results between the two sample preparation versions (DPX and d-SPE). Overall, 86% of the pesticides achieved recoveries (three spiking levels 10, 50 and 200 µg/kg) in the range of 70–120%, with <13% RSD. The matrix effects were also evaluated in both the versions and in strawberries from different crop types. Although not evidencing significant differences between the two methodologies were observed, however, the DPX cleanup proved to be a faster technique and easy to execute. The results indicate that QuEChERS with d-SPE and DPX and GC–MS/MS analysis achieved reliable quantification and identification of 36 pesticide residues in strawberries from OF and IPM.

Uso do QR no marketing digital: a perspetiva do utilizador português

Dissertação de Mestrado apresentada ao Instituto de Contabilidade e Administração do Porto para a obtenção do grau de Mestre em Marketing Digital, sob orientação de Doutor José Freitas Santos

Gestão de operações de um armazém

i Gestão de Operações de um armazém Patrícia Raquel Freitas Gomes Relatório de estágio apresentado ao Instituto Superior de Contabilidade e Administração do Porto para obtenção de Grau de Mestre em Logística Orientado por: Prof. Doutora Maria Teresa Ribeiro Pereira Coorientado por: Eng.º César Emanuel Marinho Carvalho Teixeira

Desenvolvimento de ferramentas BIM no âmbito do cálculo estrutural em situação de incêndio

Este trabalho insere-se no âmbito de um estágio curricular realizado no gabinete de projetos SE2P, durante o qual foram desenvolvidas ferramentas de cálculo estrutural em situação de incêndio, integradas numa metodologia de trabalho que segue os princípios inerentes à tecnologia BIM (Building Information Modeling). Em particular foi implementado um procedimento de análise ao fogo segundo os modelos simplificados prescritos pelos Eurocódigos. Estes modelos garantem a segurança estrutural, permitindo, de forma rápida e eficiente, a determinação das necessidades de proteção passiva para diferentes cenários, tendo em vista a obtenção da solução mais económica. Esta dissertação, para além da apresentação do trabalho desenvolvido em regime de estágio curricular, objetivou dotar o leitor de um documento que introduza os principais conceitos relativos ao cálculo estrutural em situação de incêndio, indicando as várias opções de análise e respetivas vantagens e desvantagens, ajudando a definir a sua adequabilidade ao projeto em estudo. Neste contexto é efetuada uma introdução geral ao fenómeno do fogo e às medidas mais correntes de proteção, indicando-se os documentos normativos aplicáveis tanto ao cálculo estrutural como aos materiais de proteção. É também abordada a interação entre as várias normas que devem ser consultadas quando é efetuada uma análise ao fogo, e quais se aplicam a cada fase da análise. Efetua-se uma clara distinção entre a análise do comportamento térmico e mecânico, indicando-se as principais propriedades dos materiais em função do tipo de análise e a forma como são afetadas pela temperatura. No campo da análise do comportamento térmico faz-se essencialmente referência aos modelos de cálculo simplificados do desenvolvimento da temperatura em elementos metálicos e vigas mistas, com e sem proteção passiva. No que concerne ao campo da análise do comportamento mecânico são descritos os modelos de cálculo simplificados para a verificação da segurança estrutural atendendo às ações e combinações em situação de incêndio e à perda de resistência a temperaturas elevadas. Relativamente ao trabalho desenvolvido na SE2P, relativo ao desenvolvimento de ferramentas de cálculo e a sua implementação na análise ao fogo, realiza-se uma descrição detalhada de todo o processo, e da forma como se integra no conceito BIM, utilizando informações provenientes da modelação das estruturas e introduzindo novos dados ao modelo. Realizou-se também a aplicação de todo o procedimento de análise e das ferramentas desenvolvidas, a um caso de estudo baseado num edifício de habitação. Este caso de estudo serviu também para criar cenários de otimização utilizando-se referências de preços de mercado para o aço, sua transformação em fábrica e sistemas de proteção passiva, demonstrando-se a dificuldade em encontrar caminhos rápidos e diretos de decisão no processo de otimização.

Development of paper-based color test-strip for drug detection in aquatic environment: Application to oxytetracycline

The wide use of antibiotics in aquaculture has led to the emergence of resistant microbial species. It should be avoided/minimized by controlling the amount of drug employed in fish farming. For this purpose, the present work proposes test-strip papers aiming at the detection/semi-quantitative determination of organic drugs by visual comparison of color changes, in a similar analytical procedure to that of pH monitoring by universal pH paper. This is done by establishing suitable chemical changes upon cellulose, attributing the paper the ability to react with the organic drug and to produce a color change. Quantitative data is also enabled by taking a picture and applying a suitable mathematical treatment to the color coordinates given by the HSL system used by windows. As proof of concept, this approach was applied to oxytetracycline (OXY), one of the antibiotics frequently used in aquaculture. A bottom-up modification of paper was established, starting by the reaction of the glucose moieties on the paper with 3-triethoxysilylpropylamine (APTES). The so-formed amine layer allowed binding to a metal ion by coordination chemistry, while the metal ion reacted after with the drug to produce a colored compound. The most suitable metals to carry out such modification were selected by bulk studies, and the several stages of the paper modification were optimized to produce an intense color change against the concentration of the drug. The paper strips were applied to the analysis of spiked environmental water, allowing a quantitative determination for OXY concentrations as low as 30 ng/mL. In general, this work provided a simple, method to screen and discriminate tetracycline drugs, in aquaculture, being a promising tool for local, quick and cheap monitoring of drugs.

New molecularly-imprinted polymer for carnitine and its application as ionophore in potentiometric selective membranes

Carnitine (CRT) is a biological metabolite found in urine that contributes in assessingseveral disease conditions, including cancer. Novel quick screening procedures for CRT are therefore fundamental. This work proposes a novel potentiometric device where molecularly imprinted polymers (MIPs) were used as ionophores. The host-tailored sites were imprinted on a polymeric network assembled by radical polymerization of methacrylic acid (MAA) and trimethylpropane trimethacrylate (TRIM). Non-imprinted polymers (NIPs) were produced as control by removing the template from the reaction media. The selective membrane was prepared by dispersing MIP or NIP particles in plasticizer and poly(vinyl chloride), PVC, and casting this mixture over a solid contact support made of graphite. The composition of the selective membrane was investigated with regard to kind/amount of sensory material (MIP or NIP), and the need for a lipophilic additive. Overall, MIP sensors with additive exhibited the best performance, with near-Nernstian response down to ~ 1 × 10− 4 mol L− 1, at pH 5, and a detection limitof ~ 8 × 10− 5 mol L− 1. Suitable selectivity was found for all membranes, assessed by the matched potential method against some of the most common species in urine (urea, sodium, creatinine, sulfate, fructose and hemoglobin). CRT selective membranes including MIP materials were applied successfully to the potentiometric determination of CRT in urine samples.