Electroanalytical study of the pesticide ethiofencarb

A detailed study of voltammetric behavior of ethiofencarb (ETF) is reported using glassy carbon electrode (GCE) and hanging mercury drop electrode (HMDE). With GCE, it is possible to verify that the oxidative mechanism is irreversible, independent of pH, and the maximum intensity current was observed at +1.20 V vs. AgCl/Ag at pH 1.9. A linear calibration line was obtained from 1.0x10-4 to 8.0x10-4 mol L-1 with SWV method. To complete the electrochemical knowledge of ETF pesticide, the reduction was also explored with HMDE. A well-defined peak was observed at –1.00V vs. AgCl/Ag in a large range of pH with higher signal at pH 7.0. Linearity was obtained in 4.2x10-6 and 9.4x10-6 mol L-1 ETF concentration range. An immediate alkaline hydrolysis of ETF was executed, producing a phenolic compound (2-ethylthiomethylphenol) (EMP), and the electrochemical activity of the product was examined. It was deduced that it is oxidized on GCE at +0.75V vs. AgCl/Ag with a maximum peak intensity current at pH 3.2, but the compound had no reduction activity on HMDE. Using the decrease of potential peak, a flow injection analysis (FIA) system was developed connected to an amperometric detector, enabling the determination of EMP over concentration range of 1.0x10-7 and 1.0x10-5 mol L-1 at a sampling rate of 60 h-1. The results provided by FIA methodology were performed by comparison with results from high-performance liquid chromatography (HPLC) technique and demonstrated good agreement with relative deviations lower than 4%. Recovery trials were performed and the obtained values were between 98 and 104%.

A actual conjuntura económico-financeira e os mercados de futuros sobre o petróleo

Mestrado em Contabilidade e Análise Financeira

Maltol determination in food by microwave assisted extraction and electrochemical detection

An electrochemical method is proposed for the determination of maltol in food. Microwave-assisted extraction procedures were developed to assist sample pre-treating steps. Experiments carried out in cyclic voltammetry showed an irreversible and adsorption controlled reduction of maltol. A cathodic peak was observed at -1.0 V for a Hanging Mercury Drop Electrode versus an AgCl/Ag (in saturated KCl), and the peak potential was pH independent. Square wave voltammetric procedures were selected to plot calibration curves. These procedures were carried out with the optimum conditions: pH 6.5; frequency 50 Hz; deposition potential 0.6 V; and deposition time 10 s. A linear behaviour was observed within 5.0 × 10-8 and 3.5 × 10-7 M. The proposed method was applied to the analysis of cakes, and results were compared with those obtained by an independent method. The voltammetric procedure was proven suitable for the analysis of cakes and provided environmental and economical advantages, including reduced toxicity and volume of effluents and decreased consumption of reagents.

Power law and entropy analysis of catastrophic phenomena

Catastrophic events, such as wars and terrorist attacks, tornadoes and hurricanes, earthquakes, tsunamis, floods and landslides, are always accompanied by a large number of casualties. The size distribution of these casualties has separately been shown to follow approximate power law (PL) distributions. In this paper, we analyze the statistical distributions of the number of victims of catastrophic phenomena, in particular, terrorism, and find double PL behavior. This means that the data sets are better approximated by two PLs instead of a single one. We plot the PL parameters, corresponding to several events, and observe an interesting pattern in the charts, where the lines that connect each pair of points defining the double PLs are almost parallel to each other. A complementary data analysis is performed by means of the computation of the entropy. The results reveal relationships hidden in the data that may trigger a future comprehensive explanation of this type of phenomena.

The cross crypto scheme cipher integration for securing SCADA component communication

Critical Infrastructures became more vulnerable to attacks from adversaries as SCADA systems become connected to the Internet. The open standards for SCADA Communications make it very easy for attackers to gain in-depth knowledge about the working and operations of SCADA networks. A number of Intenrnet SCADA security issues were raised that have compromised the authenticity, confidentiality, integrity and non-repudiation of information transfer between SCADA Components. This paper presents an integration of the Cross Crypto Scheme Cipher to secure communications for SCADA components. The proposed scheme integrates both the best features of symmetric and asymmetric encryptiontechniques. It also utilizes the MD5 hashing algorithm to ensure the integrity of information being transmitted.

Dimensionamento de obras de dissipação de energia em drenagem de vias de comunicação

Dissertação de Natureza Científica para obtenção do grau de Mestre em Engenharia Civil na Área de Especialização de Hidráulica

Pine processionary moth (Thaumetopoea pityocampa) and great tit (Parus major) in Portugal

In the present work, we studied a common outbreaking Lepidoptera species in Portuguese pine stands – Thaumetopoea pityocampa (Den. & Schiff.) - and one of its potential predators – Parus major (L.). The population dynamics of the immature stages of the Lepidoptera was studied in several types of Pinus pinaster (Aiton) plantations in three different areas: Setúbal Peninsula, Abrantes and National Pine Forest of Leiria. Location and plantation structure was the most important factors determining population density of T. pityocampa. Setubal and Abrantes was highly susceptible to attacks by the Lepidoptera, whereas Leiria had lower densities. Young and homogeneous pine stands was more susceptible to attacks than older and more heterogeneous pines stands. However, a desynchronized population of T. pityocampa, in which the larvae develops during summer instead of during winter, reached high densities also in Leiria. The impact of several mortality factors and climatic conditions on the immature stages of the insect (eggs and larvae), in normal and desynchronized populations are discussed, as well as possible evolutionary implications of the sudden appearance of the new version of T. pityocampa. The break of the pupa diapause and adult emergence times the annual life cycle of this insect. Adults from the desynchronized population emerged earlier than adults from the normal population, which in turn determined the change in the larvae development period. Different factors, potentially affecting the timing of adult emergence in both normal and abnormal populations are also discussed. To study P. Major, nest-boxes were placed in the areas of Setúbal and Leiria and they were monitored during three seasons. The nest-boxes increased the density of breeding and wintering birds in the studied pine plantations, indicating that a lack of natural holes are in fact a limiting factor for this populations. The earliest breeding start for this species was recorded in my study area, indicating that Portuguese coastal pines provide good breeding conditions earlier than in other areas of Europe and North Africa. This leads to an overlap between the end of the larvae stage of T. pityocampa and the beginning of the breeding season of P. major. Key-words: Thaumetopoea pityocampa, Parus major, Pinus pinaster, population dynamics, Portugal.

Phex: a computational tool for plate heat exchanges design problems

This paper presents a computational tool (PHEx) developed in Excel VBA for solving sizing and rating design problems involving Chevron type plate heat exchangers (PHE) with 1-pass-1-pass configuration. The rating methodology procedure used in the program is outlined, and a case study is presented with the purpose to show how the program can be used to develop sensitivity analysis to several dimensional parameters of PHE and to observe their effect on transferred heat and pressure drop.

Formative assessment and motivation in higher education: a successful approach in mechanical engineer thermodynamics

Between 2000/01 and 2006/07, the approval rate of a Thermodynamics course in a Mechanical Engineer graduation was 25%. However, a careful analysis of the results showed that 41% of the students chosen not to attend or dropped out, missing the final examination. Thus, a continuous assessment methodology was developed, whose purpose was to reduce drop out, motivating students to attend this course, believing that what was observed was due, not to the incapacity to pass, but to the anticipation of the inevitability of failure by the students. If, on one hand, motivation is defined as a broad construct pertaining to the conditions and processes that account for the arousal, direction, magnitude, and maintenance of effort, on the other hand, assessment is one of the most powerful tools to change the will that students have to learn, motivating them to learn in a quicker and permanent way. Some of the practices that were implemented, included: promoting learning goal orientation rather than performance goal orientation; cultivating intrinsic interest in the subject and put less emphasis on grades but make grading criteria explicit; emphasizing teaching approaches that encourage collaboration among students and cater for a range of teaching styles; explaining the reasons for, and the implications of, tests; providing feedback to students about their performance in a form that is non-egoinvolving and non-judgemental and helping students to interpret it; broadening the range of information used in assessing the attainment of individual students. The continuous assessment methodology developed was applied in 2007/08 and 2008/09, having found an increase in the approval from 25% to 55% (30%), accompanied by a decrease of the drop out from 41% to 23,5% (17,5%). Flunking with a numerical grade lowered from 34,4% to 22,0% (12,4%). The perception by the students of the continuous assessment relevance was evaluated with a questionnaire. 70% of the students that failed the course respond that, nevertheless, didn’t repent having done the continuous assessment.

Optical nonlinearity in Tandem SI-C photodetectors

The behavior of tandem pin heterojunctions based on a-SiC: H alloys is investigated under different optical and electrical bias conditions. The devices are optimized to act as optically selective wavelength filters. Depending on the device configuration (optical gaps, thickness, sequence of cells in the stack structure) and on the applied voltage (positive or negative) and optical bias (wavelength, intensity, frequency) it is possible to combine the wavelength discrimination function with the self amplification of the signal. This wavelength nonlinearity allows the amplification or the rejection of a weak signal-impulse. The device works as an active tunable optical filter for wavelength selection and can be used as an add/drop multiplexer (ADM) which enables data to enter and leave an optical network bit stream without having to demultiplex the stream. Results show that, even under weak transient input signals, the background wavelength controls the output signal. This nonlinearity, due to the transient asymmetrical light penetration of the input channels across the device together with the modification on the electrical field profile due to the optical bias, allows tuning an input channel without demultiplexing the stream. This high optical nonlinearity makes the optimized devices attractive for the amplification of all optical signals. Transfer characteristics effects due to changes in steady state light, control d.c. voltage and applied light pulses are presented. Based on the experimental results and device configuration an optoelectronic model is developed. The transfer characteristics effects due to changes in steady state light, dc control voltage or applied light pulses are simulated and compared with the experimental data. A good agreement was achieved.

Substituted P-Phenylene Ethynylene trimers as fluorescent sensors for nitroaromatic explosives

New sensory materials based on p-phenylene ethynylene trimers integrating calix[4]arene receptors (CALIX-PET) and tert-butylphenol (TBP-PET) moieties have been synthesized and their sensitivity and selectivity for the detection of nitroaromatic compounds (NACs) such as nitrobenzene (NB), 2,4-dinitrotoluene (2,4-DNT), 2,4,6-trinitrotoluene (TNT) and picric acid (PA) investigated in fluid phase and solid-state. It was found that both fluorophores displayed high sensitivities toward NACs detection in solution as evaluated by the Stern-Volmer formalism. For all the tested explosives, the ratio of fluorescence intensities (F-0/F) is a linear function of the quencher concentration only after appropriate correction of fluorescence quenching data for inner-filter effects. The quenching efficiencies for CALIX-PET and TBP-PET follow the order PA >> TNT > DNT > NB, which correlate well with the quenchers electron affinities as evaluated from their LUMOs energies thereby suggesting a photoinduced electron transfer as the dominant mechanism of fluorescence quenching. The selectivity of these sensors was checked against exemplar interferents possessing differentiated electronic properties (benzoic acid, 2,4-dichlorophenol and benzoquinone) and reduced quenching activity was detected. The quenching efficiencies and response times of the two fluorophores in the solid-state toward NB, 2,4-DNT and TNT vapors were evaluated through steady-state fluorescence quenching experiments with the materials dispersed in polymeric matrices or as neat films. The most significant fluorescence quenching responses were achieved for drop-casted films of TBP-PET upon exposure to nitroaromatics.

Liquid crystal beads constrained on thin cellulosic fibers: Electric field induced microrotors and N-I transition

We directly visualize the response of nematic liquid crystal drops of toroidal topology threaded in cellulosic fibers, suspended in air, to an AC electric field and at different temperatures over the N-I transition. This new liquid crystal system can exhibit non-trivial point defects, which can be energetically unstable against expanding into ring defects depending on the fiber constraining geometries. The director anchoring tangentially near the fiber surface and homeotropically at the air interface makes a hybrid shell distribution that in turn causes a ring disclination line around the main axis of the fiber at the center of the droplet. Upon application of an electric field, E, the disclination ring first expands and moves along the fiber main axis, followed by the appearance of a stable "spherical particle" object orbiting around the fiber at the center of the liquid crystal drop. The rotation speed of this particle was found to vary linearly with the applied voltage. This constrained liquid crystal geometry seems to meet the essential requirements in which soliton-like deformations can develop and exhibit stable orbiting in three dimensions upon application of an external electric field. On changing the temperature the system remains stable and allows the study of the defect evolution near the nematic-isotropic transition, showing qualitatively different behaviour on cooling and heating processes. The necklaces of such liquid crystal drops constitute excellent systems for the study of topological defects and their evolution and open new perspectives for application in microelectronics and photonics.

A sustentabilidade e o ciclo de vida dos edifícios

A crescente preocupação que envolve as questões ambientais a nível mundial, cada vez mais agravadas pelo comportamento irresponsável do Homem, conduziu à criação de métodos de avaliação dos impactes ambientais provocados por produtos e sistemas. Sendo o sector da construção responsável por grande parte desses impactes, é evidente a necessidade de aplicação de medidas que visem mitigar ou, no mínimo, reduzir até valores aceitáveis, essas agressões ao meio ambiente. Nesse âmbito, é natural que tenha surgido a ideia de aplicar uma metodologia tão precisa e rigorosa como a LCA ao sector da construção. No entanto, nos dias de hoje, as preocupações alargaram-se às vertentes social e económica que, juntamente com a vertente ambiental, formam o triângulo de equilíbrio do desenvolvimento sustentável. É precisamente essa avaliação tripartida que esta Dissertação pretende abordar, tentando aprofundar conhecimentos e fornecer alternativas, através da análise crítica, que possam contribuir para a melhoria contínua desta metodologia.

Project, modelling and simulation of air stripping columns for the treatment of groundwater contaminated with volatile organic compounds

Volatile organic compounds are a common source of groundwater contamination that can be easily removed by air stripping in columns with random packing and using a counter-current flow between the phases. This work proposes a new methodology for the column design for any particular type of packing and contaminant avoiding the necessity of a pre-defined diameter used in the classical approach. It also renders unnecessary the employment of the graphical Eckert generalized correlation for pressure drop estimates. The hydraulic features are previously chosen as a project criterion and only afterwards the mass transfer phenomena are incorporated, in opposition to conventional approach. The design procedure was translated into a convenient algorithm using C++ as programming language. A column was built in order to test the models used either in the design or in the simulation of the column performance. The experiments were fulfilled using a solution of chloroform in distilled water. Another model was built to simulate the operational performance of the column, both in steady state and in transient conditions. It consists in a system of two partial non linear differential equations (distributed parameters). Nevertheless, when flows are steady, the system became linear, although there is not an evident solution in analytical terms. In steady state the resulting system of ODE can be solved, allowing for the calculation of the concentration profile in both phases inside the column. In transient state the system of PDE was numerically solved by finite differences, after a previous linearization.

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.