Soil remediation time to achieve clean-up goals I: influence of soil water content

The current models are not simple enough to allow a quick estimation of the remediation time. This work reports the development of an easy and relatively rapid procedure for the forecasting of the remediation time using vapour extraction. Sandy soils contaminated with cyclohexane and prepared with different water contents were studied. The remediation times estimated through the mathematical fitting of experimental results were compared with those of real soils. The main objectives were: (i) to predict, through a simple mathematical fitting, the remediation time of soils with water contents different from those used in the experiments; (ii) to analyse the influence of soil water content on the: (ii1) remediation time; (ii2) remediation efficiency; and (ii3) distribution of contaminants in the different phases present into the soil matrix after the remediation process. For sandy soils with negligible contents of clay and natural organic matter, artificially contaminated with cyclohexane before vapour extraction, it was concluded that (i) if the soil water content belonged to the range considered in the experiments with the prepared soils, then the remediation time of real soils of similar characteristics could be successfully predicted, with relative differences not higher than 10%, through a simple mathematical fitting of experimental results; (ii) increasing soil water content from 0% to 6% had the following consequences: (ii1) increased remediation time (1.8–4.9 h, respectively); (ii2) decreased remediation efficiency (99–97%, respectively); and (ii3) decreased the amount of contaminant adsorbed onto the soil and in the non-aqueous liquid phase, thus increasing the amount of contaminant in the aqueous and gaseous phases.

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.

A capacidade de subitizing em crianças de 4 anos

Dissertação apresentada à escola Superior de Educação de Lisboa para obtenção de grau de mestre em Educação Matemática na Educação Pré-Escolar e nos 1º e 2º Ciclos do Ensino Básico

Flow-injection potentiometric method for the routine determination of chloride: application to bread analysis

Bread is consumed worldwide by man, thus contributing to the regular ingestion of certain inorganic species such as chloride. It controls the blood pressure if associated to a sodium intake and may increase the incidence of stomach ulcer. Its routine control should thus be established by means of quick and low cost procedures. This work reports a double- channel flow injection analysis (FIA) system with a new chloride sensor for the analysis of bread. All solutions are prepared in water and necessary ionic strength adjustments are made on-line. The body of the indicating electrode is made from a silver needle of 0.8 mm i.d. with an external layer of silver chloride. These devices were constructed with different lengths. Electrodes of 1.0 to 3.0 cm presented better analytical performance. The calibration curves under optimum conditions displayed Nernstian behaviour, with average slopes of 56 mV decade-1, with sampling rates of 60 samples h-1. The method was applied to analyze several kinds of bread, namely pão de trigo, pão integral, pão de centeio, pão de mistura, broa de milho, pão sem sal, pão meio sal, pão-de-leite, and pão de água. The accuracy and precision of the potentiometric method were ascertained by comparison to a spectrophotometric method of continuous segmented flow. These methods were validated against ion-chromatography procedures.

Social contextual factors contributing to child and adolescent labor: an ecological analysis

OBJECTIVE: To examine the relationship between social contextual factors and child and adolescent labor. METHODS: Population-based cohort study carried out with 2,512 families living in 23 subareas of a large urban city in Brazil from 2000 to 2002. A random one-stage cluster sampling was used to select families. Data were obtained through individual household interviews using questionnaires. The annual cumulative incidence of child and adolescent labor was estimated for each district. New child and adolescent labor cases were those who had their first job over the two-year follow-up. The annual cumulative incidence of child and adolescent labor was the response variable and predictors were contextual factors such as lack of social support, social deprivation, unstructured family, perceived violence, poor school quality, poor environment conditions, and poor public services. Pearson's correlation and multiple linear regression were used to assess the associations. RESULTS: There were selected 943 families corresponding to 1,326 non-working children and adolescents aged 8 to 17 years. Lack of social support, social deprivation, perceived violence were all positively and individually associated with the annual cumulative incidence of child and adolescent labor. In the multiple linear regression model, however, only lack of social support and perceived violence in the neighborhood were positively associated to child and adolescent labor. No effect was found for poor school quality, poor environment conditions, poor public services or unstructured family. CONCLUSIONS: Poverty reduction programs can reduce the contextual factors associated with child and adolescent labor. Violence reduction programs and strengthening social support at the community level may contribute to reduce CAL.

Estudo da implementação da filosofia Lean na indústria Portuguesa

A forte competitividade dos mercados a nível nacional e internacional tem levado muitas empresas a estudar métodos e técnicas de incremento à eliminação dos desperdícios, à redução de custos e tempos, ao aumento da qualidade e da flexibilidade, tendo a filosofia lean um papel crucial na prossecução destes objectivos. Desde os seus primórdios, a avaliação da implementação da filosofia lean no universo das empresas é uma questão de investigação na área de conhecimento da gestão industrial. Embora a nível individual as diferentes empresas possam quantificar e avaliar os resultados da aplicação do lean, a grande dificuldade surge quando se pretende obter uma comparação por sector ou tipo de actividade económica. Existem países onde a prática do lean tem sido prioritária e as empresas ocupam a vanguarda nesta área de conhecimento. No entanto, em Portugal, existe uma clara dificuldade em se determinar até que ponto o tecido empresarial português assimilou esta filosofia e que resultados têm obtido com a prática do lean. Este trabalho apresenta um estudo realizado a partir de um inquérito, obtido através de um questionário on-line, às empresas que operam em Portugal de forma a estudar e analisar o estado actual do lean em Portugal e antever tendências futuras numa perspectiva de evolução da aplicação desta metodologia de gestão de processos produtivos. Em resultado deste estudo foi possível identificar quais são os grandes obstáculos à introdução do lean, áreas em que se observou sucesso ou menor impacto e quais as ferramentas e técnicas mais usadas por sector. Como resultado deste estudo é convicção do autor que foi possível obter uma fotografia abrangente do actual estado de implementação do lean e desta forma caracterizar as áreas que seguem na vanguarda da implementação do lean, e as áreas que ainda apresentam um desenvolvimento incipiente. Desta forma parece ao autor que o presente estudo apresenta grande utilidade para o mundo académico bem como para o tecido empresarial português.

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).

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.

As características de um líder que permitem mudar uma cultura empresarial

Mestrado em Gestão e Empreendedorismo

HFCs e soluções alternativas viáveis

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

Red light (Processo contra-ordenacional em meio urbano)

Devido ao acréscimo significativo de viaturas e peões nas grandes cidades foi necessário recorrer aos mecanismos existentes para coordenar o tráfego. Nesta perspectiva surge a implementação de semáforos com o objectivo de ordenar o tráfego nas vias rodoviárias. A gestão de tráfego, tem sido sujeita a inovações tanto ao nível dos equipamentos, do software usado, gestão centralizada, monitorização das vias e na sincronização semafórica, sendo possível a criação de programas ajustados às diferentes exigências de tráfego verificadas durante as vinte e quatro horas para pontos distintos da cidade. Conceptualmente foram elaborados estudos, com o objectivo de identificar a relação entre a velocidade o fluxo e o intervalo num determinado intervalo de tempo, bem como a relação entre a velocidade e a sinistralidade. Até 1995 Portugal era um dos países com maior número de sinistros rodoviários Na sequência desta evolução foram instalados radares de controlo de velocidade no final de 2006 com o objectivo de obrigar ao cumprimento dos limites de velocidade impostos pelo código da estrada e reduzir a sinistralidade automóvel na cidade de Lisboa. Passados alguns anos sobre o investimento realizadoanteriormente, constatamos que existe a necessidade de implementar novas tecnologias na detecção das infracções, sejam estas de excesso de velocidade ou violação do semáforo vermelho (VSV), optimizar a informação disponibilizada aos automobilistas e aos peões, coordenar a interacção entre os veículos prioritários e os restantes presentes na via, dinamizar a gestão interna das contra ordenações, agilizar os procedimentos informatizar a recolha deinformação de modo a tornar os processos mais céleres.

Projeto de uma instalação frigorífica

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

Entity localization and tracking: a sensor fusion-based mechanism in WSNs

Knowing exactly where a mobile entity is and monitoring its trajectory in real-time has recently attracted a lot of interests from both academia and industrial communities, due to the large number of applications it enables, nevertheless, it is nowadays one of the most challenging problems from scientific and technological standpoints. In this work we propose a tracking system based on the fusion of position estimations provided by different sources, that are combined together to get a final estimation that aims at providing improved accuracy with respect to those generated by each system individually. In particular, exploiting the availability of a Wireless Sensor Network as an infrastructure, a mobile entity equipped with an inertial system first gets the position estimation using both a Kalman Filter and a fully distributed positioning algorithm (the Enhanced Steepest Descent, we recently proposed), then combines the results using the Simple Convex Combination algorithm. Simulation results clearly show good performance in terms of the final accuracy achieved. Finally, the proposed technique is validated against real data taken from an inertial sensor provided by THALES ITALIA.

Dimensioning and worst-case analysis of cluster-tree sensor networks

Modeling the fundamental performance limits of Wireless Sensor Networks (WSNs) is of paramount importance to understand their behavior under the worst-case conditions and to make the appropriate design choices. This is particular relevant for time-sensitive WSN applications, where the timing behavior of the network protocols (message transmission must respect deadlines) impacts on the correct operation of these applications. In that direction this paper contributes with a methodology based on Network Calculus, which enables quick and efficient worst-case dimensioning of static or even dynamically changing cluster-tree WSNs where the data sink can either be static or mobile. We propose closed-form recurrent expressions for computing the worst-case end-to-end delays, buffering and bandwidth requirements across any source-destination path in a cluster-tree WSN. We show how to apply our methodology to the case of IEEE 802.15.4/ZigBee cluster-tree WSNs. Finally, we demonstrate the validity and analyze the accuracy of our methodology through a comprehensive experimental study using commercially available technology, namely TelosB motes running TinyOS.

Sistemas de arrefecimento de instalações frigoríficas utilizando três agentes frigoríficos

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