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.

Mixed extractant systems for metal recovery

Hoje em dia, a prevenção dos resíduos de metais é uma questão muito importante para um grande número de empresas, pois necessitam optimizar o seu sistema de tratamento de águas residuais a fim de alcançarem os limites legais dos teores em iões metálicos e poderem efectuar a descarga das águas residuais no domínio hídrico público. Devido a esta problemática foram efectuados estudos inovadores relacionados com a remoção de iões metálicos de águas residuais, verificando-se que as tecnologias de membrana oferecem uma série de vantagens para o efeito. Uma dessas tecnologias, referida como Membrana Líquida de Suporte (SLM), é baseada num mecanismo de extracção. A membrana hidrofóbica, impregnada com uma solução extractora, funciona como barreira entre a água residual e uma solução, geralmente ácida. A diferença de pH entre a água residual e a solução actua como força motriz para o transporte de iões metálicos da água residual para a referida solução. Poderá ocorrer um problema de falta de estabilidade, resultante da possível fuga da solução extractora para fora dos poros das membranas. Estudos anteriores mostraram que os ácidos alquilfosfóricos ou ácidos fosfónicos, como os reagentes D2EHPA e CYANEX e hidroxioximas como o LIX 860-I podem ser muito úteis para a extração de iões metálicos como ferro, cobre, níquel, zinco e outros. A clássica extracção líquido-líquido também tem mostrado que a mistura de diferentes extractores pode ter um efeito sinergético. No entanto, não é claro que haja um efeito óptimo da razão de extractor ou que tipo de complexo é formado durante o processo de extracção. O objectivo deste projecto é investigar este comportamento sinergético e as complexas formações por meio de um método espectrofotométrico, o “Job’s method” e “Mole-ratio method”. Estes métodos são utilizados para estimar a estequiometria dos vários complexos entre dois solutos, a partir da variação de absorvância dos complexos quando comparado com a absorvância do soluto. Com este projecto, o Job’s method e mole-ratio method serão aplicados a um sistema de três componentes, para conseguir mais informações sobre a complexação de níquel (II) e a fim de determinar a razão extractor: metal dos complexos formados durante a aplicação de mistura de extractores D2EHPA e LIX 860-I. Segundo Job’s method a elavada absorvância situa-se na região de 0,015-0,040 M de LIX 860-I e uma baixa concentração de D2EHPA. Quando as diferentes experiências são encontradas num conjunto experimental foram avaliadas de acordo com o método de trabalho, o valor máximo do gráfico foi encontrado para uma baixa fração molar do ião metálico e uma maior concentração de D2EHPA. Esta mudança foi encontrado de 0,50 até 0,30, que poderia apontar para a direção da formação de diferentes complexos. Para o Mole-Ratio method, a estequiometria dos complexos metal pode ser determinada a partir do ponto de intersecção das linhas tangente do gráfico da absorbância versus a concentração do ligante. Em todos os casos, o máximo foi obtido em torno de uma concentração total de 0,010 M. Quando D2EHPA foi aplicado sozinho, absorvâncias muito baixos foram obtidas.

Actuador linear para teste de teclas na indústria automóvel

As indústrias de componentes e acessórios automóveis são um elo fundamental no processo produtivo da indústria automóvel. Neste leque industrial encontra-se a Preh Portugal, Lda, como empresa fornecedora de componentes electrónicos, mais concretamente, painéis de controlo de climatização. Os painéis fornecidos pela Preh aos seus clientes encontram-se sujeitos a rigorosos testes de qualidade e funcionalidade. Neste sentido o teste funcional das teclas surge, relacionando o curso da tecla em função de uma força actuante. Esta relação está comprometida com uma curva característica padrão para o tipo de tecla. Para além destes compromissos, também é necessário que a tecla feche e abra o seu contacto eléctrico. Esta tese foca-se no desenvolvimento do teste de teclas, apresentando uma alteração ao sistema actual com a introdução de um sistema embebido, no intuito de flexibilizar o sistema de teste e reduzindo custos. O sistema embebido pretende dar capacidade de processamento ao teste e, desta forma, substituir o actual computador como elemento de processamento. A solução implementada consistiu numa mudança estrutural, através da inclusão do sistema embebido entre o computador e o sistema de deslocamento. Passando o foco central do processo de teste a residir no sistema embebido, este tem de estabelecer comunicações com os restantes elementos intervenientes no teste. Estabelece comunicações série RS-232 com o sistema de deslocamento (leitura do curso e força na tecla), Ethernet com o computador (comandos, parâmetros e resultados) e CAN com o painel de controlo de climatização (fecho/abertura do contacto eléctrico). A concretização deste projecto resultou numa nova estrutura e aplicação, a qual é facilmente integrada na linha de produção com as vantagens de ser menos onerosa e mais flexível, conforme o pretendido.

Determinação de propriedades mecânicas através de ensaios de provetes miniatura, "Small Punch"

Trabalho Final de Mestrado para obtenção do grau de Mestre em Engenharia Mecânica

Magnetic and plagioclase linear fabric discrepancy in dykes: a new way to define the flow vector using magnetic foliation

In basaltic dykes the magnetic lineation K1 (maximum magnetic susceptibility axis) is generally taken to indicate the flow direction during solidification of the magma. This assumption was tested in Tertiary basaltic dykes from Greenland displaying independent evidence of subhorizontal flow. The digital processing of microphotographs from thin sections cut in (K1, K2) planes yields the preferred linear orientation of plagioclase, which apparently marks the magma flow lineation. In up to 60% of cases, the angular separation between K1 and the assumed flow direction is greater than 45degrees. This suggests that the uncorroborated use of magnetic lineations in dykes is risky. A simple geometrical method is proposed to infer the flow vector from AMS in dykes based solely on magnetic foliations.

Signal Subspace Identification in Hyperspectral Linear Mixtures

Chpater in Book Proceedings with Peer Review Second Iberian Conference, IbPRIA 2005, Estoril, Portugal, June 7-9, 2005, Proceedings, Part II

Vertex component analysis: a fast algorithm to extract endmembers spectra from hyperspectral data

Chapter in Book Proceedings with Peer Review First Iberian Conference, IbPRIA 2003, Puerto de Andratx, Mallorca, Spain, JUne 4-6, 2003. Proceedings

Vertex component analysis: a fast algorithm to unmix hyperspectral data

Given a set of mixed spectral (multispectral or hyperspectral) vectors, linear spectral mixture analysis, or linear unmixing, aims at estimating the number of reference substances, also called endmembers, their spectral signatures, and their abundance fractions. This paper presents a new method for unsupervised endmember extraction from hyperspectral data, termed vertex component analysis (VCA). The algorithm exploits two facts: (1) the endmembers are the vertices of a simplex and (2) the affine transformation of a simplex is also a simplex. In a series of experiments using simulated and real data, the VCA algorithm competes with state-of-the-art methods, with a computational complexity between one and two orders of magnitude lower than the best available method.

Parallel implementation of vertex component analysis for hyperspectral endmember extraction

International Conference with Peer Review 2012 IEEE International Conference in Geoscience and Remote Sensing Symposium (IGARSS), 22-27 July 2012, Munich, Germany

Criticality of colloids with distinct interaction patches: The limits of linear chains, hyperbranched polymers, and dimers

We use a simple model of associating fluids which consists of spherical particles having a hard-core repulsion, complemented by three short-ranged attractive sites on the surface (sticky spots). Two of the spots are of type A and one is of type B; the bonding interactions between each pair of spots have strengths epsilon(AA), epsilon(BB), and epsilon(AB). The theory is applied over the whole range of bonding strengths and the results are interpreted in terms of the equilibrium cluster structures of the phases. In addition to our numerical results, we derive asymptotic expansions for the free energy in the limits for which there is no liquid-vapor critical point: linear chains (epsilon(AA)not equal 0, epsilon(AB)=epsilon(BB)=0), hyperbranched polymers (epsilon(AB)not equal 0, epsilon(AA)=epsilon(BB)=0), and dimers (epsilon(BB)not equal 0, epsilon(AA)=epsilon(AB)=0). These expansions also allow us to calculate the structure of the critical fluid by perturbing around the above limits, yielding three different types of condensation: of linear chains (AA clusters connected by a few AB or BB bonds); of hyperbranched polymers (AB clusters connected by AA bonds); or of dimers (BB clusters connected by AA bonds). Interestingly, there is no critical point when epsilon(AA) vanishes despite the fact that AA bonds alone cannot drive condensation.

Square-wave voltametric method for determination of molinate concentration in a biological process using a hanging mercury drop electrode

A square-wave voltammetric (SWV) method using a hanging mercury drop electrode (HMDE) has been developed for determination of the herbicide molinate in a biodegradation process. The method is based on controlled adsorptive accumulation of molinate for 10 s at a potential of -0.8 V versus AgCl/Ag. An anodic peak, due to oxidation of the adsorbed pesticide, was observed in the cyclic voltammogram at ca. -0.320 V versus AgCl/Ag; a very small cathodic peak was also detected. The SWV calibration plot was established to be linear in the range 5.0x10-6 to 9.0x10-6 mol L-1; this corresponded to a detection limit of 3.5x10-8 mol L-1. This electroanalytical method was used to monitor the decrease of molinate concentration in river waters along a biodegradation process using a bacterial mixed culture. The results achieved with this voltammetric method were compared with those obtained by use of a chromatographic method (HPLC–UV) and no significant statistical differences were observed.

Quantification of endocrine disruptors and pesticides in water by gas chromatography–tandem mass spectrometry. Method validation using weighted linear regression schemes

Amulti-residue methodology based on a solid phase extraction followed by gas chromatography–tandem mass spectrometry was developed for trace analysis of 32 compounds in water matrices, including estrogens and several pesticides from different chemical families, some of them with endocrine disrupting properties. Matrix standard calibration solutions were prepared by adding known amounts of the analytes to a residue-free sample to compensate matrix-induced chromatographic response enhancement observed for certain pesticides. Validation was done mainly according to the International Conference on Harmonisation recommendations, as well as some European and American validation guidelines with specifications for pesticides analysis and/or GC–MS methodology. As the assumption of homoscedasticity was not met for analytical data, weighted least squares linear regression procedure was applied as a simple and effective way to counteract the greater influence of the greater concentrations on the fitted regression line, improving accuracy at the lower end of the calibration curve. The method was considered validated for 31 compounds after consistent evaluation of the key analytical parameters: specificity, linearity, limit of detection and quantification, range, precision, accuracy, extraction efficiency, stability and robustness.

Impact of academic exposure on health status of university students

OBJECTIVE: To assess the impact of academic life on health status of university students. METHODS: Longitudinal study including 154 undergraduate students from the Universidade de Aveiro, Portugal, with at least two years of follow-up observations. Sociodemographic and behavioral characteristics were collected using questionnaires. Students' weight, height, blood pressure, serum glucose, serum lipids and serum homocysteine levels were measured. Regression analysis was performed using linear mixed-effect models, allowing for random effects at the participant level. RESULTS: A higher rate of dyslipidemia (44.0% vs. 28.6%), overweight (16.3% vs. 12.5%) and smoking (19.3% vs. 0.0%) was found among students exposed to the academic life when compared to freshmen. Physical inactivity was about 80%. Total cholesterol, high density lipoprotein-cholesterol (HDL-C), triglycerides, systolic blood pressure, and physical activity levels were significantly associated with gender (p<0.001). Academic exposure was associated with increased low density lipoprotein-cholesterol (LDL-C) levels (about 1.12 times), and marginally with total cholesterol levels (p=0.041). CONCLUSIONS: High education level does not seem to have a protective effect favoring a healthier lifestyle and being enrolled in health-related areas does not seem either to positively affect students' behaviors. Increased risk factors for non-transmissible diseases in university students raise concerns about their well-being. These results should support the implementation of health promotion and prevention programs at universities.

FIA potentiometric system based on periodate polymeric membrane sensors for the assessment of ascorbic acid in commercial drinks

Ascorbic acid is found in many food samples. Its clinical and technological importance demands an easyto- use, rapid, robust and inexpensive method of analysis. For this purpose, this work proposes a new flow procedure based on the oxidation of ascorbic acid by periodate. A new potentiometric periodate sensor was constructed to monitor this reaction. The selective membranes were of PVC with porphyrin-based sensing systems and a lipophilic cation as additive. The sensor displayed a near-Nernstian response for periodate over 1.0x10-2–6.0x10-6 M, with an anionic slope of 73.9 ± 0.9 mV decade-1. It was pH independent in acidic media and presented good selectivity features towards several inorganic anions. The flow set-up operated in double-channel, carrying a 5.0x10-4 M IO- 4 solution and a suitable buffer; these were mixed in a 50-cm reaction coil. The overall flow rate was 7 ml min-1 and the injection volume 70 µl. Under these conditions, a linear behaviour against concentration was observed for 17.7–194.0 µg ml-1, presenting slopes of 0.169 mV (mg/l)-1, a reproducibility of ±1.1 mV (n = 5), and a sampling rate of ~96 samples h-1. The proposed method was applied to the analysis of beverages and pharmaceuticals.

New insights on integer-programming models for the kidney exchange problem

In recent years several countries have set up policies that allow exchange of kidneys between two or more incompatible patient–donor pairs. These policies lead to what is commonly known as kidney exchange programs. The underlying optimization problems can be formulated as integer programming models. Previously proposed models for kidney exchange programs have exponential numbers of constraints or variables, which makes them fairly difficult to solve when the problem size is large. In this work we propose two compact formulations for the problem, explain how these formulations can be adapted to address some problem variants, and provide results on the dominance of some models over others. Finally we present a systematic comparison between our models and two previously proposed ones via thorough computational analysis. Results show that compact formulations have advantages over non-compact ones when the problem size is large.