Dimensionamento de muros de suporte considerando diferentes metodologias de cálculo

A presente dissertação consiste em verificar a tendência do coeficiente de segurança quando se varia certos parâmetros (ângulo de atrito interno do terreno, inclinação do terrapleno no tardoz do muro e o ângulo que a massa de solo faz quando se comporta como parte integrante do muro numa situação limite) considerados no cálculo. Para atingir os objectivos anteriormente referidos, dividiu-se o trabalho em duas fases, a primeira fase teve como objectivo verificar qual a tendência do coeficiente de segurança quando sujeito à variação de dois parâmetros, o ângulo de atrito interno do terreno e a inclinação do terrapleno no tardoz do muro que varia de 5° até ao valr do ângulo de atrito interno do terreno. A segunda fase consiste em analisar qual a tendência do coeficiente de segurança quando sujeito à variação de três parâmetros, o ângulo de atrito interno do terreno, de 20° a 45°, a inclinação do terrapleno no tardoz do muro, de 10° até ao valor do ângulo de atrito interno do terreno, e o ângulo que a massa de solo faz quando se comporta como parte integrante do muro numa situação limite. Para ambas as situações efectuaram-se os respectivos cálculos quer pela Teoria de Rankine e quer pela Teoria de Mohr – Coulomb, havendo casos em que foi necessário conjugar estas duas Teorias.

Screening of grapes and wine for azoxystrobin, kresoxim-methyl and trifloxystrobin fungicides by HPLC with diode array detection

The Quinone outside Inhibitors (QoI) are one of the most important and recent fungicide groups used in viticulture and also allowed by Integrated Pest Management. Azoxystrobin, kresoxim-methyl and trifloxystrobin are the main active ingredients for treating downy and powdery mildews that can be present in grapes and wines. In this paper, a method is reported for the analysis of these three QoI-fungicides in grapes and wine. After liquid–liquid extraction and a clean-up on commercial silica cartridges, analysis was by isocratic HPLC with diode array detection (DAD) with a run time of 13 min. Confirmation was by solid-phase micro-extraction (SPME), followed by GC/MS determination. The main validation parameters for the three compounds in grapes and wine were a limit of detection up to 0.073mg kg-1, a precision not exceeding 10.0% and an average recovery of 93% ±38.

Garantias financeiras no setor segurador

Dissertação de Mestrado apresentado ao Instituto de Contabilidade e Administração do Porto para a obtenção do grau de Mestre em Contabilidade e Finanças, sob orientação de Mestre Armindo Licínio da Silva Macedo

Técnicas de rating em contexto de crise no setor bancário português

Dissertação para a obtenção do Grau de Mestre em Contabilidade e Finanças Orientador: Mestre Adalmiro Álvaro Malheiro de Castro Andrade Pereira

Imparidade de ativos fixos tangíveis: aspetos contabilísticos, fiscais e de auditoria

Dissertação apresentada ao Instituto Superior de Contabilidade e Administração do Porto para a obtenção do grau de Mestre em Auditoria Orientada por: Mestre Carlos Martins

Sistema de Visão Stereo Ativo aplicado aos robôs do ISePorto

A presente dissertação endereça o desenvolvimento de um sistema de visão stereo ativo para os robôs de futebol robótico da equipa ISePorto do ISEP, de modo a que estes tirem o máximo partido das câmaras rotativas neles existentes. Este trabalho surge da necessidade de melhorar a capacidade de perceção do ambiente por parte dos robôs, principalmente da perceção da bola quando não está no plano do campo e dos robôs adversários. Esta necessidade surge devido ao aumento da dinâmica que se tem vindo a veri car ultimamente nas competições. Para tal, foram estudados algumas trabalhos relacionados no que diz respeito a sistemas de visão stereo com baselines variáveis e eixos de rotação em ambas as câmaras, bem como fundamentos de visão stereo. Foi proposta uma arquitetura para o sistema de visão ativo de modo a ser aplicado em qualquer robô da equipa MSL (Middle Size League). Para tornar possível a implementação desta arquitetura foi desenvolvido um procedimento para a calibração e determinação em tempo real dos parâmetros extrínsecos do par stereo em função da posição angular dos eixos rotativos do robô. O sistema de visão foi também dotado de capacidade de sincronismo e foram implementadas funcionalidades ao nível de software que possibilitam a deteção de objetos na imagem, a correspondência de objetos presentes nas imagens de ambas as câmaras e consequentemente a determinação das posições tridimensionais desses objetos relativamente ao robô. O sistema desenvolvido foi testado e validado em cenário MSL ao nível de perceção da bola, robôs adversários e linhas do campo. Os resultados obtidos apresentam uma melhoria signi cativa, face à implementação atual dos robôs, na perceção tridimensional da bola quando não está no plano do campo, e dos robôs adversários.

Occurrence of bisphenol A, estrone, 17b-estradiol and 17a-ethinylestradiol in Portuguese rivers

This study focused on the occurrence of several EDCs including bisphenol A, estrone (E1), the 17b-estradiol (E2) and 17a- thinylestradiol (EE2) in fourteen rivers of Portugal. Samples analysis revealed a widespread contamination of BPA especially in Ave, Cávado, Douro, Ferro, Sousa and Vizela Rivers. Achieving 98.4 ng/L for the highest concentration. The estrogens achieved above the method quantification limit (MQL) were E1 in Águeda River and E2 in Ave, Lima and Tâmega Rivers. The maximum concentration detected for E1 was 26.9 ng/L. EE2 was detected only below MQL.

Biosensor based on multi-walled carbon nanotubes paste electrode modified with laccase for pirimicarb pesticide quantification

This study focused on the development of a sensitive enzymatic biosensor for the determination of pirimicarb pesticide based on the immobilization of laccase on composite carbon paste electrodes. Multi- walled carbon nanotubes(MWCNTs)paste electrode modified by dispersion of laccase(3%,w/w) within the optimum composite matrix(60:40%,w/w,MWCNTs and paraffin binder)showed the best performance, with excellent electron transfer kinetic and catalytic effects related to the redox process of the substrate4- aminophenol. No metal or anti-interference membrane was added. Based on the inhibition of laccase activity, pirimicarb can be determined in the range 9.90 ×10- 7 to 1.15 ×10- 5 molL 1 using 4- aminophenol as substrate at the optimum pH of 5.0, with acceptable repeatability and reproducibility (relative standard deviations lower than 5%).The limit of detection obtained was 1.8 × 10-7 molL 1 (0.04 mgkg 1 on a fresh weight vegetable basis).The high activity and catalytic properties of the laccase- based biosensor are retained during ca. one month. The optimized electroanalytical protocol coupled to the QuEChERS methodology were applied to tomato and lettuce samples spiked at three levels; recoveries ranging from 91.0±0.1% to 101.0 ± 0.3% were attained. No significant effects in the pirimicarb electro- analysis were observed by the presence of pro-vitamin A, vitamins B1 and C,and glucose in the vegetable extracts. The proposed biosensor- based pesticide residue methodology fulfills all requisites to be used in implementation of food safety programs.

Molinate quantification in environmental water by a glutathione-S-transferase based biosensor

A glutathione-S-transferase (GST)based biosensor was developed to quantify the thiocarbamate herbicide molinate in environmental water.The biosensor construction was based on GST immobilization onto a glassy carbon electrode via aminosilane–glutaraldehyde covalent attachment. The principle supporting the use of this biosensor consists of the GST inhibition process promoted by molinate. Differential pulse voltammetry was used to obtain a calibration curve for molinate concentration, ranging from 0.19 to 7.9 mgL -1 and presenting a detection limit of 0.064 mgL- 1. The developed biosensor is stable,and reusable during 15 days.The GST-based biosensor was successfully applied to quantify molinate in rice paddy field floodwater samples. The results achieved with the developed biosensor were in accordance with those obtained by high performance liquid chromatography. The proposed device is suitable for screening environmental water analysis and, since no sample preparation is required, it can be used in situ and in real-time measurements.

Determination of methiocarb and Its degradation products, methiocarb sulfoxide and methiocarb sulfone, in bananas using QuEChERS extraction

The present work describes the development of an analytical method for the determination of methiocarb and its degradation products (methiocarb sulfoxide and methiocarb sulfone) in banana samples, using the QuEChERS (quick, easy, cheap, effective, rugged, and safe) procedure followed by liquid chromatography coupled to photodiode array detector (LCPAD). Calibration curves were linear in the range of 0.5−10 mg L−1 for all compounds studied. The average recoveries, measured at 0.1 mg kg−1 wet weight, were 92.0 (RSD = 1.8%, n = 3), 84.0 (RSD = 3.9%, n = 3), and 95.2% (RSD = 1.9%, n = 3) for methiocarb sulfoxide, methiocarb sulfone, and methiocarb, respectively. Banana samples treated with methiocarb were collected from an experimental field. The developed method was applied to the analysis of 24 samples (peel and pulp) and to 5 banana pulp samples. Generally, the highest levels were found for methiocarb sulfoxide and methiocarb. Methiocarb sulfone levels were below the limit of quantification, except in one sample (not detected).

Multiresidue pesticides analysis in soils using modified QuEChERS with disposable pipette extraction and dispersive solid-phase extraction

QuEChERS original method was modified into a new version for pesticides determination in soils. The QuEChERS method is based on liquid–liquid portioning with ACN and was followed by cleanup step using dispersive SPE and disposable pipette tips. Gas chromatographic separation with MS detection was carried out for pesticides quantification. The method was validated using recovery experiments for 36 multiclass pesticides. Mean recoveries of pesticides at each of the four spiking levels between 10–300 µg/kg of soil ranged from 70–120% for 26 pesticides with RSD values less than 15%. The method achieved low limit of detection less than 7.6 µ g/kg. Matrix effects were observed for 13 pesticides. Matrix effects were compensated by using matrix-matched calibration. The method was applied successfully using d-SPE or DPX in the analysis of the pesticides in soils from organic farming and integrated pest management.

Optimization of QuEChERS procedure coupled to GC-ECD for organochlorine pesticide determination in carrot samples

An optimised version of the Quick, Easy, Cheap, Effective, Rugged and Safe (QuEChERS) method for simultaneous determination of 14 organochlorine pesticides in carrots was developed using gas chromatography coupled with electron-capture detector (GC-ECD) and confirmation by gas chromatography tandem mass spectrometry (GC-MS/MS). A citrate-buffered version of QuEChERS was applied for the extraction of the organochlorine pesticides, and for the extract clean-up, primary secondary amine, octadecyl-bonded silica (C18), magnesium sulphate (MgSO4) and graphitized carbon black were used as sorbents. The GC-ECD determination of the target compounds was achieved in less than 20 min. The limits of detection were below the EUmaximum residue limits (MRLs) for carrots, 10–50 μg kg−1, while the limit of quantification did exceed 10 μg kg−1 for hexachlorobenzene (HCB). The introduction of a sonication step was shown to improve the recoveries. The overall average recoveries in carrots, at the four tested levels (60, 80, 100 and 140 μg kg−1), ranged from 66 to 111% with relative standard deviations in the range of 2– 15 % (n03) for all analytes, with the exception of HCB. The method has been applied to the analysis of 21 carrot samples from different Portuguese regions, and β-HCH was the pesticide most frequently found, with concentrations oscillating between less than the limit of quantification to 14.6 μg kg−1. Only one sample had a pesticide residue (β-HCH) above the MRL, 14.6 μg kg−1. This methodology combines the advantages of both QuEChERS and GC-ECD, producing a very rapid, sensitive and reliable procedure which can be applied in routine analytical laboratories.

Determination of ochratoxin A in bread: evaluation of microwave-assisted extraction using an orthogonal composite design coupled with response surface methodology

An analytical method using microwave-assisted extraction (MAE) and liquid chromatography (LC) with fluorescence detection (FD) for the determination of ochratoxin A (OTA) in bread samples is described. A 24 orthogonal composite design coupled with response surface methodology was used to study the influence of MAE parameters (extraction time, temperature, solvent volume, and stirring speed) in order to maximize OTA recovery. The optimized MAE conditions were the following: 25 mL of acetonitrile, 10 min of extraction, at 80 °C, and maximum stirring speed. Validation of the overall methodology was performed by spiking assays at five levels (0.1–3.00 ng/g). The quantification limit was 0.005 ng/g. The established method was then applied to 64 bread samples (wheat, maize, and wheat/maize bread) collected in Oporto region (Northern Portugal). OTAwas detected in 84 % of the samples with a maximum value of 2.87 ng/g below the European maximum limit established for OTA in cereal products of 3 ng/g.

Forest fires in Northern region of Portugal: impact on PM levels

Every year European citizens become victims of devastating fires, which are especially disastrous for Southern European countries. Apart from the numerous health and economic consequences, fires generate hazardous pollutants that are introduced into the environment, thus representing serious risks for public health. In that regard, particulate matter (PM) is of amajor concern. Thus, the objectives of thisworkwere to characterize the trend of forest fire occurrences and burnt area during the period of 2005 and 2010 and to study the influence of forest fires on levels of particulatematter PM10 and PM2.5. In 2010, 22,026 forest fires occurred in Portugal. The northern region was the most affected by forest fires, with 27% of occurrences in Oporto district. The annual means of PM10 and PM2.5 concentrations at two urban background sites were 25±14 μg m−3 and 8.2±4.9 μg m−3, and 17±13 μg m−3 and 7.3±5.9 μg m−3, respectively. At both sites the highest levels of PMfractionswere observed during July and August of 2010, corresponding to the periods when majority (66%) of forest fires occurred. Furthermore, PM10 daily limit at the two sites was exceeded during 20 and 5 days, respectively; 56%, and respectively 60% of those exceedances occurred during the forest fire season. Considering that the risks of forest fire ignition and severity are enhanced with elevated temperatures, the climate change might increase the environmental impacts of forest fires.

PAH air pollution at a Portuguese urban area: carcinogenic risks and sources identification

This study aimed to characterize air pollution and the associated carcinogenic risks of polycyclic aromatic hydrocarbon (PAHs) at an urban site, to identify possible emission sources of PAHs using several statistical methodologies, and to analyze the influence of other air pollutants and meteorological variables on PAH concentrations.The air quality and meteorological data were collected in Oporto, the second largest city of Portugal. Eighteen PAHs (the 16 PAHs considered by United States Environment Protection Agency (USEPA) as priority pollutants, dibenzo[a,l]pyrene, and benzo[j]fluoranthene) were collected daily for 24 h in air (gas phase and in particles) during 40 consecutive days in November and December 2008 by constant low-flow samplers and using polytetrafluoroethylene (PTFE) membrane filters for particulate (PM10 and PM2.5 bound) PAHs and pre-cleaned polyurethane foam plugs for gaseous compounds. The other monitored air pollutants were SO2, PM10, NO2, CO, and O3; the meteorological variables were temperature, relative humidity, wind speed, total precipitation, and solar radiation. Benzo[a]pyrene reached a mean concentration of 2.02 ngm−3, surpassing the EU annual limit value. The target carcinogenic risks were equal than the health-based guideline level set by USEPA (10−6) at the studied site, with the cancer risks of eight PAHs reaching senior levels of 9.98×10−7 in PM10 and 1.06×10−6 in air. The applied statistical methods, correlation matrix, cluster analysis, and principal component analysis, were in agreement in the grouping of the PAHs. The groups were formed according to their chemical structure (number of rings), phase distribution, and emission sources. PAH diagnostic ratios were also calculated to evaluate the main emission sources. Diesel vehicular emissions were the major source of PAHs at the studied site. Besides that source, emissions from residential heating and oil refinery were identified to contribute to PAH levels at the respective area. Additionally, principal component regression indicated that SO2, NO2, PM10, CO, and solar radiation had positive correlation with PAHs concentrations, while O3, temperature, relative humidity, and wind speed were negatively correlated.