The development and optimization of a modified single-drop microextraction method for organochlorine pesticides determination by gas chromatography-tandem mass spectrometry

We have developed a new method for single-drop microextraction (SDME) for the preconcentration of organochlorine pesticides (OCP) from complex matrices. It is based on the use of a silicone ring at the tip of the syringe. A 5 μL drop of n-hexane is applied to an aqueous extract containing the OCP and found to be adequate to preconcentrate the OCPs prior to analysis by GC in combination with tandem mass spectrometry. Fourteen OCP were determined using this technique in combination with programmable temperature vaporization. It is shown to have many advantages over traditional split/splitless injection. The effects of kind of organic solvent, exposure time, agitation and organic drop volume were optimized. Relative recoveries range from 59 to 117 %, with repeatabilities of <15 % (coefficient of variation) were achieved. The limits of detection range from 0.002 to 0.150 μg kg−1. The method was applied to the preconcentration of OCPs in fresh strawberry, strawberry jam, and soil.

Optimization of QuEChERS method for the analysis of organochlorine pesticides in soils with diverse organic matter

A QuEChERS method has been developed for the determination of 14 organochlorine pesticides in 14 soils from different Portuguese regions with wide range composition. The extracts were analysed by GC-ECD (where GC-ECD is gas chromatography-electron-capture detector) and confirmed by GC-MS/MS (where MS/MS is tandem mass spectrometry). The organic matter content is a key factor in the process efficiency. An optimization was carried out according to soils organic carbon level, divided in two groups: HS (organic carbon>2.3%) and LS (organic carbon<2.3%). Themethod was validated through linearity, recovery, precision and accuracy studies. The quantification was carried out using a matrixmatched calibration to minimize the existence of the matrix effect. Acceptable recoveries were obtained (70–120%) with a relative standard deviation of ≤16% for the three levels of contamination. The ranges of the limits of detection and of the limits of quantification in soils HS were from 3.42 to 23.77 μg kg−1 and from 11.41 to 79.23 μg kg−1, respectively. For LS soils, the limits of detection ranged from 6.11 to 14.78 μg kg−1 and the limits of quantification from 20.37 to 49.27 μg kg−1. In the 14 collected soil samples only one showed a residue of dieldrin (45.36 μg kg−1) above the limit of quantification. This methodology combines the advantages of QuEChERS, GC-ECD detection and GC-MS/MS confirmation producing a very rapid, sensitive and reliable procedure which can be applied in routine analytical laboratories.

Salt content in bread and dough from northern Portugal: method development and comparison

In the initial stage of this work, two potentiometric methods were used to determine the salt (sodium chloride) content in bread and dough samples from several cities in the north of Portugal. A reference method (potentiometric precipitation titration) and a newly developed ion-selective chloride electrode (ISE) were applied. Both methods determine the sodium chloride content through the quantification of chloride. To evaluate the accuracy of the ISE, bread and respective dough samples were analyzed by both methods. Statistical analysis (0.05 significance level) indicated that the results of these methods did not differ significantly. Therefore the ISE is an adequate alternative for the determination of chloride in the analyzed samples. To compare the results of these chloride-based methods with a sodium-based method, sodium was quantified in the same samples by a reference method (atomic absorption spectrometry). Significant differences between the results were verified. In several cases the sodium chloride content exceeded the legal limit when the chloride-based methods were used, but when the sodium-based method was applied this was not the case. This could lead to the erroneous application of fines and therefore the authorities should supply additional information regarding the analytical procedure for this particular control.

Selecção do melhor descolorante para a eliminação da cor residual num efluente têxtil

Mestrado em Engenharia Química

An Interface to Retrieve Personal Memories Using an Iconic Visual Language

Relevant past events can be remembered when visualizing related pictures. The main difficulty is how to find these photos in a large personal collection. Query definition and image annotation are key issues to overcome this problem. The former is relevant due to the diversity of the clues provided by our memory when recovering a past moment and the later because images need to be annotated with information regarding those clues to be retrieved. Consequently, tools to recover past memories should deal carefully with these two tasks. This paper describes a user interface designed to explore pictures from personal memories. Users can query the media collection in several ways and for this reason an iconic visual language to define queries is proposed. Automatic and semi-automatic annotation is also performed using the image content and the audio information obtained when users show their images to others. The paper also presents the user interface evaluation based on tests with 58 participants.

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.

Assesing multileaf collimator effect on the build-up region using Monte Carlo method

Previous Monte Carlo studies have investigated the multileaf collimator (MLC) contribution to the build-up region for fields in which the MLC leaves were fully blocking the openings defined by the collimation jaws. In the present work, we investigate the same effect but for symmetric and asymmetric MLC defined field sizes (2×2, 4×4, 10×10 and 3×7 cm2). A Varian 2100C/D accelerator with 120-leaf MLC is accurately modeled fora6MVphoton beam using the BEAMnrc/EGSnrc code. Our results indicate that particles scattered from accelerator head and MLC are responsible for the increase of about 7% on the surface dose when comparing 2×2 and 10×10 cm2 fields. We found that the MLC contribution to the total build-up dose is about 2% for the 2×2 cm2 field and less than 1% for the largest fields.

Expert opinion on best practice guidelines and competency framework for visual screening in children

PURPOSE: Screening programs to detect visual abnormalities in children vary among countries. The aim of this study is to describe experts' perception of best practice guidelines and competency framework for visual screening in children. METHODS: A qualitative focus group technique was applied during the Portuguese national orthoptic congress to obtain the perception of an expert panel of 5 orthoptists and 2 ophthalmologists with experience in visual screening for children (mean age 53.43 years, SD ± 9.40). The panel received in advance a script with the description of three tuning competencies dimensions (instrumental, systemic, and interpersonal) for visual screening. The session was recorded in video and audio. Qualitative data were analyzed using a categorical technique. RESULTS: According to experts' views, six tests (35.29%) have to be included in a visual screening: distance visual acuity test, cover test, bi-prism or 4/6(Δ) prism, fusion, ocular movements, and refraction. Screening should be performed according to the child age before and after 3 years of age (17.65%). The expert panel highlighted the influence of the professional experience in the application of a screening protocol (23.53%). They also showed concern about the false negatives control (23.53%). Instrumental competencies were the most cited (54.09%), followed by interpersonal (29.51%) and systemic (16.4%). CONCLUSIONS: Orthoptists should have professional experience before starting to apply a screening protocol. False negative results are a concern that has to be more thoroughly investigated. The proposed framework focuses on core competencies highlighted by the expert panel. Competencies programs could be important do develop better screening programs.

Global and local detection of liver steatosis from ultrasound

Liver steatosis is a common disease usually associated with social and genetic factors. Early detection and quantification is important since it can evolve to cirrhosis. Steatosis is usually a diffuse liver disease, since it is globally affected. However, steatosis can also be focal affecting only some foci difficult to discriminate. In both cases, steatosis is detected by laboratorial analysis and visual inspection of ultrasound images of the hepatic parenchyma. Liver biopsy is the most accurate diagnostic method but its invasive nature suggest the use of other non-invasive methods, while visual inspection of the ultrasound images is subjective and prone to error. In this paper a new Computer Aided Diagnosis (CAD) system for steatosis classification and analysis is presented, where the Bayes Factor, obatined from objective intensity and textural features extracted from US images of the liver, is computed in a local or global basis. The main goal is to provide the physician with an application to make it faster and accurate the diagnosis and quantification of steatosis, namely in a screening approach. The results showed an overall accuracy of 93.54% with a sensibility of 95.83% and 85.71% for normal and steatosis class, respectively. The proposed CAD system seemed suitable as a graphical display for steatosis classification and comparison with some of the most recent works in the literature is also presented.

Fatty liver characterization and classification by ultrasound

Steatosis, also known as fatty liver, corresponds to an abnormal retention of lipids within the hepatic cells and reflects an impairment of the normal processes of synthesis and elimination of fat. Several causes may lead to this condition, namely obesity, diabetes, or alcoholism. In this paper an automatic classification algorithm is proposed for the diagnosis of the liver steatosis from ultrasound images. The features are selected in order to catch the same characteristics used by the physicians in the diagnosis of the disease based on visual inspection of the ultrasound images. The algorithm, designed in a Bayesian framework, computes two images: i) a despeckled one, containing the anatomic and echogenic information of the liver, and ii) an image containing only the speckle used to compute the textural features. These images are computed from the estimated RF signal generated by the ultrasound probe where the dynamic range compression performed by the equipment is taken into account. A Bayes classifier, trained with data manually classified by expert clinicians and used as ground truth, reaches an overall accuracy of 95% and a 100% of sensitivity. The main novelties of the method are the estimations of the RF and speckle images which make it possible to accurately compute textural features of the liver parenchyma relevant for the diagnosis.

Sistema de visão para percepção e navegação de um UAV Quadrotor

Mestrado em Engenharia Electrotécnica e de Computadores

Lipid extractions from marine deep-sea invertebrates : modifications to the Bligh & Dyer method to increase lipid yields

The deep-sea environment is difficult to sample, and often only small quantities of samples can be obtained when using less destructive methods than dredging. When working with marine animals that are difficult to sample and with limited quantities of tissue to extract lipids, it is essential to ensure that the used method extracts the maximum possible quantity of lipids. This study evaluates the efficiency of introducing modifications to the method originally described by Bligh & Dyer (1959). This lipid extraction method is broadly used with modifications, although these usually lack proper description and evaluation of increment in lipids. In this study we consider the improvement in terms of amount of lipids extracted by changing the method. Lipid content was determined by gravimetric measurements in eight invertebrates from the deep-sea, including deep-sea hydrothermal vents animals, using three different approaches. Results show increases of 14% to 30% in lipid contents obtained from hydrothermal vent invertebrate tissues and whole animals by placing the samples in methanol for 24 hours before applying the Bligh & Dyer mixture. Efficiency of the extractions using frozen and freeze-dried samples was also compared. For large sponges, the use of lyophilized materials resulted in increases of 3 to 7 times more lipids extracted when compared with extractions using frozen samples.

Plataforma de gestão de incidentes

Mestrado em Engenharia Electrotécnica e de Computadores. Área de Especialização de Telecomunicações.

Contrastive terminology: semitic, anglo-germanic and latin concept building through complex terms. (avoiding one-way method procedures in translation

This paper aims to present a contrastive approach between three different ways of building concepts after proving the similar syntactic possibilities that coexist in terms. However, from the semantic point of view we can see that each language family has a different distribution in meaning. But the most important point we try to show is that the differences found in the psychological process when communicating concepts should guide the translator and the terminologist in the target text production and the terminology planning process. Differences between languages in the information transmission process are due to the different roles the different types of knowledge play. We distinguish here the analytic-descriptive knowledge and the analogical knowledge among others. We also state that none of them is the best when determining the correctness of a term, but there has to be adequacy criteria in the selection process. This concept building or term building success is important when looking at the linguistic map of the information society.