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.

Electrochemical methods in pesticides control

The state of the art of voltammetric and amperometric methods used in the study and determination of pesticides in crops, food, phytopharmaceutical products, and environmental samples is reviewed. The main structural groups of pesticides, i.e., triazines, organophosphates, organochlorides, nitrocompounds, carbamates, thiocarbamates, sulfonylureas, and bipyridinium compounds are considered with some degradation products. The advantages, drawbacks, and trends in the development of voltammetric and amperometric methods for study and determination of pesticides in these samples are discussed.

Hearing evaluation of portuguese school communities: school‑based audiology and hearing screening

Introduction: Hearing loss h sone raised impact in the development and academic progress of a child. In several developed countries, early detection is part of the national health plan through universal neonatal hearing screening (UNHS) and also with school hearing screening programs (SHSP), but only a few have published national data and revised protocols. Currently in Portugal, the UNHS is implemented in the main district hospitals but not the SHPS, as well we still do not make use of concrete data nor publication of studies on the national reality. Objectives: The incidence of the hearing loss and of otological problems was studied in school communities in the north of the country with 2550 participants between 3 and 17 years old. Methods: Statistical data collected within the schools with a standard auditory hearing screening protocol. All participants were evaluated with the same protocol, an audiological anamnesis, otoscopy and audiometric exam screening (500, 1000, 2000 and 4000 Hz) were fulfilled. Results: Different otological problems were identified and the audiometric screening exam counted auditory thresholds that outpointed uni and bilateral hearing loss in about 5.7% of the cases. Conclusions: The study has demonstrated that auditory school screening should take place as early as possible and be part of the primary health care to identify and direct children to appropriate rehabilitation, education and attendance. Thus, reducing high costs with late treatment.

Bisphenol A migration from plastic materials: direct insight of ecotoxicity in Daphnia magna

Bisphenol A (BPA) is an endocrine disrupting chemical (EDC) whose migration from food packaging is recognized worldwide. However, the real overall food contamination and related consequences are yet largely unknown. Among humans, children’s exposure to BPA has been emphasized because of the immaturity of their biological systems. The main aim of this study was to assess the reproductive impact of BPA leached from commercially available plastic containers used or related to child nutrition, performing ecotoxicological tests using the biomonitoring species Daphnia magna. Acute and chronic tests, as well as single and multigenerational tests were done. Migration of BPA from several baby bottles and other plastic containers evaluated by GC-MS indicated that a broader range of foodstuff may be contaminated when packed in plastics. Ecotoxicological test results performed using defined concentrations of BPA were in agreement with literature, although a precocious maturity of daphnids was detected at 3.0 mg/L. Curiously, an increased reproductive output (neonates per female) was observed when daphnids were bred in the polycarbonate (PC) containers (145.1±4.3 % to 264.7±3.8 %), both in single as in multigenerational tests, in comparison with the negative control group (100.3±1.6 %). A strong correlated dose-dependent ecotoxicological effect was observed, providing evidence that BPA leached from plastic food packaging materials act as functional estrogen in vivo at very low concentrations. In contrast, neonate production by daphnids cultured in polypropylene and non-PC bottles was slightly but not significantly enhanced (92.5±2.0 % to 118.8±1.8 %). Multigenerational tests also revealed magnification of the adverse effects, not only on fecundity but also on mortality, which represents a worrying trend for organisms that are chronically exposed to xenoestrogens for many generations. Two plausible explanations for the observed results could be given: a non-monotonic dose–response relationship or a mixture toxicity effect.

Evaluation of distinct input methods of an intelligent wheelchair in simulated and real environments: a performance and usability study

This paper focuses on evaluating the usability of an Intelligent Wheelchair (IW) in both real and simulated environments. The wheelchair is controlled at a high-level by a flexible multimodal interface, using voice commands, facial expressions, head movements and joystick as its main inputs. A Quasi-experimental design was applied including a deterministic sample with a questionnaire that enabled to apply the System Usability Scale. The subjects were divided in two independent samples: 46 individuals performing the experiment with an Intelligent Wheelchair in a simulated environment (28 using different commands in a sequential way and 18 with the liberty to choose the command); 12 individuals performing the experiment with a real IW. The main conclusion achieved by this study is that the usability of the Intelligent Wheelchair in a real environment is higher than in the simulated environment. However there were not statistical evidences to affirm that there are differences between the real and simulated wheelchairs in terms of safety and control. Also, most of users considered the multimodal way of driving the wheelchair very practical and satisfactory. Thus, it may be concluded that the multimodal interfaces enables very easy and safe control of the IW both in simulated and real environments.

Local fractional variational iteration and decomposition methods for wave equation on cantor sets within local fractional operators

We perform a comparison between the fractional iteration and decomposition methods applied to the wave equation on Cantor set. The operators are taken in the local sense. The results illustrate the significant features of the two methods which are both very effective and straightforward for solving the differential equations with local fractional derivative.

Fracture toughness determination of adhesive and co-cured joints in natural fibre composites

Adhesive bonding has become more efficient in the last few decades due to the adhesives developments, granting higher strength and ductility. On the other hand, natural fibre composites have recently gained interest due to the low cost and density. It is therefore essential to predict the fracture behavior of joints between these materials, to assess the feasibility of joining or repairing with adhesives. In this work, the tensile fracture toughness (Gc n) of adhesive joints between natural fibre composites is studied, by bonding with a ductile adhesive and co-curing. Conventional methods to obtain Gc n are used for the co-cured specimens, while for the adhesive within the bonded joint, the J-integral is considered. For the J-integral calculation, an optical measurement method is developed for the evaluation of the crack tip opening and adherends rotation at the crack tip during the test, supported by a Matlab sub-routine for the automated extraction of these quantities. As output of this work, an optical method that allows an easier and quicker extraction of the parameters to obtain Gc n than the available methods is proposed (by the J-integral technique), and the fracture behaviour in tension of bonded and co-cured joints in jute-reinforced natural fibre composites is also provided for the subsequent strength prediction. Additionally, for the adhesively- bonded joints, the tensile cohesive law of the adhesive is derived by the direct method.

Caracterização molecular da resistência a antimicrobianos em Escherichia coli produtoras de β-lactamases de espectro alargado isoladas em cães e estudo da partilha de clones bacterianos entre animais de companhia e coabitantes humanos

A pressão seletiva originada pelo uso excessivo de antimicrobianos na medicina humana e veterinária tem contribuído para a emergência de estirpes bacterianas multirresistentes, sendo os estudos mais escassos relativamente à sua presença nos animais de companhia. Porque os animais e os seus proprietários partilham o mesmo espaço habitacional, apresentando comportamentos de contacto próximo, existe uma hipótese elevada de transferência microbiana inter-espécie. Ante esta possibilidade é importante escrutinar o papel dos animais de companhia enquanto reservatórios de estirpes e de genes de resistência, bem como a sua envolvência na disseminação de estirpes bacterianas multirresistentes. Importa também, investigar o papel das superfícies e objetos domésticos partilhados por ambos, como potenciadores deste fenómeno. O objetivo deste trabalho foi, identificar o filogrupo e fazer a caracterização molecular dos genes que conferem resistência aos β-lactâmicos e às quinolonas, em quarenta isolados de Escherichia coli produtoras de β-lactamases de espectro alargado (ESBL), obtidas em zaragatoas fecais de cães consultados no Hospital Veterinário do ICBAS-UP. Complementarmente pretendeu-se inferir sobre a partilha de clones de Escherichia coli e Enterococcus spp. com elevadas resistências, em cinco agregados familiares (humanos e seus animais de companhia) assim como avaliar a potencial disseminação de estirpes multirresistentes no ambiente doméstico. Previamente foram recolhidas zaragatoas de fezes, pelo e mucosa oral dos animais e em alguns casos, dos seus proprietários, e ainda do ambiente doméstico. As zaragatoas foram processadas e as estirpes isoladas com base em meios seletivos. Foram realizados testes de suscetibilidade antimicrobiana de modo a estabelecer o fenótipo de resistência de cada isolado. O DNA foi extraído por varias metodologias e técnicas de PCR foram utilizadas para caracterização de filogrupos (Escherichia coli) e identificação da espécie (Enterococcus spp.). A avaliação da proximidade filogenética entre isolados foi efetuada por ERIC PCR e PFGE. No conjunto de quarenta isolados produtores de ESBL e/ou resistentes a quinolonas verificou-se que 47,5% pertenciam ao filogrupo A, havendo uma menor prevalência do filogrupo D (25,0%), B1 (17,5%), e B2 (10,0%).A frequência de resistência nestes isolados é factualmente elevada, sendo reveladora de uma elevada pressão seletiva. Com exceção de dois isolados, os fenótipos foram justificados pela presença de β-lactamases. A frequência da presença de genes foi: 47% blaTEM, 34% blaSHV, 24% blaOXA , 18% blaCTX-M-15, 8% blaCTX-M-2, 3% blaCTX-M-9. Nos isolados resistentes às quinolonas verificou-se maioritariamente a presença de mutações nos genes cromossomais gyrA e parC, e em alguns casos a presença de um determinante de resistência mediado por plasmídeo – qnrS. Nos cinco “agregados familiares” (humanos e animais) estudados foi observada uma partilha frequente de clones de E. coli e Enterococcus faecalis com múltiplas resistências, isolados em fezes e mucosa oral de cães e gatos e fezes e mãos dos respetivos proprietários, evidenciando-se assim uma possível transferência direta entre coabitantes (agregados A, C, D, E). Ficou também comprovado com percentagens de similaridade genotípica superiores a 94% que essa disseminação também ocorre para o ambiente doméstico, envolvendo objetos dos animais e de uso comum (agregados A, E). Os resultados obtidos reforçam a necessidade de um uso prudente dos antimicrobianos, pois elevados padrões de resistências terão um impacto não só na qualidade de vida dos animais mas também na saúde humana. Adicionalmente importa sensibilizar os proprietários para a necessidade de uma maior vigilância relativamente às formas de interação com os animais, bem como para a adoção de medidas higiénicas cautelares após essa mesma interação.

Damage evaluation of drilled carbon/epoxy laminates based on area assessment methods

The characteristics of carbon fibre reinforced laminates had widened their use, from aerospace to domestic appliances. A common characteristic is the need of drilling for assembly purposes. It is known that a drilling process that reduces the drill thrust force can decrease the risk of delamination. In this work, delamination assessment methods based on radiographic data are compared and correlated with mechanical test results (bearing test).

RSS and LEA adaptation for indoor location using fingerprinting

Fingerprinting is an indoor location technique, based on wireless networks, where data stored during the offline phase is compared with data collected by the mobile device during the online phase. In most of the real-life scenarios, the mobile node used throughout the offline phase is different from the mobile nodes that will be used during the online phase. This means that there might be very significant differences between the Received Signal Strength values acquired by the mobile node and the ones stored in the Fingerprinting Map. As a consequence, this difference between RSS values might contribute to increase the location estimation error. One possible solution to minimize these differences is to adapt the RSS values, acquired during the online phase, before sending them to the Location Estimation Algorithm. Also the internal parameters of the Location Estimation Algorithms, for example the weights of the Weighted k-Nearest Neighbour, might need to be tuned for every type of terminal. This paper focuses both approaches, using Direct Search optimization methods to adapt the Received Signal Strength and to tune the Location Estimation Algorithm parameters. As a result it was possible to decrease the location estimation error originally obtained without any calibration procedure.

Improvement of a filters method in a derivative free optimization

Constraints nonlinear optimization problems can be solved using penalty or barrier functions. This strategy, based on solving the problems without constraints obtained from the original problem, have shown to be e ective, particularly when used with direct search methods. An alternative to solve the previous problems is the lters method. The lters method introduced by Fletcher and Ley er in 2002, , has been widely used to solve problems of the type mentioned above. These methods use a strategy di erent from the barrier or penalty functions. The previous functions de ne a new one that combine the objective function and the constraints, while the lters method treat optimization problems as a bi-objective problems that minimize the objective function and a function that aggregates the constraints. Motivated by the work of Audet and Dennis in 2004, using lters method with derivative-free algorithms, the authors developed works where other direct search meth- ods were used, combining their potential with the lters method. More recently. In a new variant of these methods was presented, where it some alternative aggregation restrictions for the construction of lters were proposed. This paper presents a variant of the lters method, more robust than the previous ones, that has been implemented with a safeguard procedure where values of the function and constraints are interlinked and not treated completely independently.

A survey of technologies and applications for climbing robots locomotion and adhesion

The interest in the development of climbing robots has grown rapidly in the last years. Climbing robots are useful devices that can be adopted in a variety of applications, such as maintenance and inspection in the process and construction industries. These systems are mainly adopted in places where direct access by a human operator is very expensive, because of the need for scaffolding, or very dangerous, due to the presence of an hostile environment. The main motivations are to increase the operation efficiency, by eliminating the costly assembly of scaffolding, or to protect human health and safety in hazardous tasks. Several climbing robots have already been developed, and other are under development, for applications ranging from cleaning to inspection of difficult to reach constructions. A wall climbing robot should not only be light, but also have large payload, so that it may reduce excessive adhesion forces and carry instrumentations during navigation. These machines should be capable of travelling over different types of surfaces, with different inclinations, such as floors, walls, or ceilings, and to walk between such surfaces (Elliot et al. (2006); Sattar et al. (2002)). Furthermore, they should be able of adapting and reconfiguring for various environment conditions and to be self-contained. Up to now, considerable research was devoted to these machines and various types of experimental models were already proposed (according to Chen et al. (2006), over 200 prototypes aimed at such applications had been developed in the world by the year 2006). However, we have to notice that the application of climbing robots is still limited. Apart from a couple successful industrialized products, most are only prototypes and few of them can be found in common use due to unsatisfactory performance in on-site tests (regarding aspects such as their speed, cost and reliability). Chen et al. (2006) present the main design problems affecting the system performance of climbing robots and also suggest solutions to these problems. The major two issues in the design of wall climbing robots are their locomotion and adhesion methods. With respect to the locomotion type, four types are often considered: the crawler, the wheeled, the legged and the propulsion robots. Although the crawler type is able to move relatively faster, it is not adequate to be applied in rough environments. On the other hand, the legged type easily copes with obstacles found in the environment, whereas generally its speed is lower and requires complex control systems. Regarding the adhesion to the surface, the robots should be able to produce a secure gripping force using a light-weight mechanism. The adhesion method is generally classified into four groups: suction force, magnetic, gripping to the surface and thrust force type. Nevertheless, recently new methods for assuring the adhesion, based in biological findings, were proposed. The vacuum type principle is light and easy to control though it presents the problem of supplying compressed air. An alternative, with costs in terms of weight, is the adoption of a vacuum pump. The magnetic type principle implies heavy actuators and is used only for ferromagnetic surfaces. The thrust force type robots make use of the forces developed by thrusters to adhere to the surfaces, but are used in very restricted and specific applications. Bearing these facts in mind, this chapter presents a survey of different applications and technologies adopted for the implementation of climbing robots locomotion and adhesion to surfaces, focusing on the new technologies that are recently being developed to fulfill these objectives. The chapter is organized as follows. Section two presents several applications of climbing robots. Sections three and four present the main locomotion principles, and the main "conventional" technologies for adhering to surfaces, respectively. Section five describes recent biological inspired technologies for robot adhesion to surfaces. Section six introduces several new architectures for climbing robots. Finally, section seven outlines the main conclusions.

A comparative analysis of fault injection methods via enhanced on-chip debug infrastructures

On-chip debug (OCD) features are frequently available in modern microprocessors. Their contribution to shorten the time-to-market justifies the industry investment in this area, where a number of competing or complementary proposals are available or under development, e.g. NEXUS, CJTAG, IJTAG. The controllability and observability features provided by OCD infrastructures provide a valuable toolbox that can be used well beyond the debugging arena, improving the return on investment rate by diluting its cost across a wider spectrum of application areas. This paper discusses the use of OCD features for validating fault tolerant architectures, and in particular the efficiency of various fault injection methods provided by enhanced OCD infrastructures. The reference data for our comparative study was captured on a workbench comprising the 32-bit Freescale MPC-565 microprocessor, an iSYSTEM IC3000 debugger (iTracePro version) and the Winidea 2005 debugging package. All enhanced OCD infrastructures were implemented in VHDL and the results were obtained by simulation within the same fault injection environment. The focus of this paper is on the comparative analysis of the experimental results obtained for various OCD configurations and debugging scenarios.

Assessment of direct radiological risk and indirect associated toxic risks originated by Coal-Fired Power Plants

Over the past few decades there has been some discussion concerning the increase of the natural background radiation originated by coal-fired power plants, due to the uranium and thorium content present in combustion ashes. The radioactive decay products of uranium and thorium, such as radium, radon, polonium, bismuth and lead, are also released in addition to a significant amount of 40K. Since the measurement of radioactive elements released by the gaseous emissions of coal power plants is not compulsory, there is a gap of information concerning this situation. Consequently, the prediction of dispersion and mobility of these elements in the environment, after their release, is based on limited data and the radiological impact from the exposure to these radioactive elements is unknown. This paper describes the methodology that is being developed to assess the radiological impact due to the raise in the natural background radiation level originated by the release and dispersion of the emitted radionuclides. The current investigation is part of a research project that is undergoing in the vicinity of Sines coal-fired power plant (south of Portugal) until 2013. Data from preliminary stages are already available and possible of interpretation.

Auditoria de resultados no Ministério da Defesa Nacional, ramo Exército

Trabalho de Projeto apresentado ao Instituto de Contabilidade e Administração do Porto para a obtenção do grau de Mestre em Auditoria, sob orientação do Dr. Rodrigo Carvalho e co-orientação do Major de Artilharia António Rabaço