Analysis of six fungicides and one acaricide in still and fortified wines using solid-phase microextraction-gas chromatography/tandem mass spectrometry

A multiresidue gas chromatographic method for the determination of six fungicides (captan, chlorthalonil, folpet, iprodione, procymidone and vinclozolin) and one acaricide (dicofol) in still and fortified wines was developed. Solid-phase microextraction (SPME) was chosen for the extraction of the compounds from the studied matrices and tandem mass spectrometry (MS/MS) detection was used. The extraction consists in a solvent free and automated procedure and the detection is highly sensitive and selective. Good linearity was obtained with correlation coefficients of regression (R2) > 0.99 for all the compounds. Satisfactory results of repeatability and intermediate precision were obtained for most of the analytes (RSD < 20%). Recoveries from spiked wine ranged from 80.1% to 112.0%. Limits of quantification (LOQs) were considerably below the proposedmaximumresidue limits (MRLs) for these compounds in grapes and below the suggested limits for wine (MRLs/10), with the exception of captan.

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.

Mass spectrometry parameters optimization for the 46 multiclass pesticides determination in strawberries with gas chromatography ion-trap tandem mass spectrometry

Multiclass analysis method was optimized in order to analyze pesticides traces by gas chromatography with ion-trap and tandem mass spectrometry (GC-MS/MS). The influence of some analytical parameters on pesticide signal response was explored. Five ion trap mass spectrometry (IT-MS) operating parameters, including isolation time (IT), excitation voltage (EV), excitation time (ET),maximum excitation energy or “q” value (q), and isolationmass window (IMW) were numerically tested in order to maximize the instrument analytical signal response. For this, multiple linear regression was used in data analysis to evaluate the influence of the five parameters on the analytical response in the ion trap mass spectrometer and to predict its response. The assessment of the five parameters based on the regression equations substantially increased the sensitivity of IT-MS/MS in the MS/MS mode. The results obtained show that for most of the pesticides, these parameters have a strong influence on both signal response and detection limit.Using the optimized method, a multiclass pesticide analysis was performed for 46 pesticides in a strawberry matrix. Levels higher than the limit established for strawberries by the European Union were found in some samples.

Abordagem prática para execução de taludes em obras rodoviárias com recurso a pré‐corte

Este trabalho é realizado no domínio das obras de engenharia, área onde o desmonte de rocha com recurso a explosivos em obras rodoviárias é uma actividade específica e consistiu no acompanhamento e execução de três obras rodoviárias de média e grande dimensão. A necessidade de executar escavações, recorrendo a técnicas de desmonte cuidadoso de contorno, onde o plano de corte do talude final deve obedecer a requisitos de localização, alinhamento, inclinação, estabilidade e também estéticos, acrescendo a isto a necessidade de optimizar os meios envolvidos, obriga a que esta actividade seja encarada de uma forma sistematizada, visando o racional aproveitamento de recursos. A execução desta actividade requer conhecimentos no domínio das técnicas de desmonte de contorno, dos explosivos, do mecanismo de rotura de rochas, da operação de perfuração e da geomecânica dos maciços. A abordagem deste trabalho incide sobre a técnica denominada de pré‐corte e tem como objectivo encontrar uma equação característica que permita relacionar diferentes parâmetros envolvidos nesta actividade. Este objectivo é alcançado recorrendo à correlação entre equações relativas à pressão de detonação, à pressão no furo e ao espaçamento entre furos consecutivos, desenvolvidas por outros autores. Desta forma obteve‐se uma equação que relaciona parâmetros relativos ao maciço rochoso (resistência à tracção), ao explosivo (velocidade de detonação e densidade) e ao diagrama de fogo (concentração de carga – volume de explosivo e comprimento do furo – volume do furo). A comparação entre os valores destes parâmetros obtidos na produção e os obtidos com recurso à equação característica permite concluir que a sua aplicação para execução de futuras obras possibilita uma optimização dos meios envolvidos.

Geotecnia urbana da zona ribeirinha de Vila Nova de Gaia (Cais de Gaia, Santa Marinha – Lavadores, Canidelo): uma avaliação preliminar

Mestrado em Engenharia Geotécnica e Geoambiente

Development and validation of a novel method for the analysis of chlorinated pesticides in soils using microwave-assisted extraction–headspace solid phase microextraction and gas chromatography–tandem mass spectrometry

A new procedure for determining eleven organochlorine pesticides in soils using microwave-assisted extraction (MAE) and headspace solid phase microextraction (HS-SPME) is described. The studied pesticides consisted of mirex, α- and γ-chlordane, p,p’-DDT, heptachlor, heptachlor epoxide isomer A, γ-hexachlorocyclohexane, dieldrin, endrin, aldrine and hexachlorobenzene. The HS-SPME was optimized for the most important parameters such as extraction time, sample volume and temperature. The present analytical procedure requires a reduced volume of organic solvents and avoids the need for extract clean-up steps. For optimized conditions the limits of detection for the method ranged from 0.02 to 3.6 ng/g, intermediate precision ranged from 14 to 36% (as CV%), and the recovery from 8 up to 51%. The proposed methodology can be used in the rapid screening of soil for the presence of the selected pesticides, and was applied to landfill soil samples.

Multiresidue method for the determination of organophosphorus pesticides in still wine and fortified wine using solid-phase microextraction and gas chromatography – Tandem mass spectrometry

A SPME-GC-MS/MS method for the determination of eight organophosphorus pesticides (azinphos-methyl, chlorpyriphos, chlorpyriphos-methyl, diazinon, fenitrothion, fenthion, malathion, and methidathion) in still and fortified wine was developed. The extraction procedure is simple, solvent free, and without any sample pretreatment. Limits of detection (LOD) and quantitation (LOQ) values in the range 0.1–14.3 lg/L and 0.2–43.3 lg/L, respectively, were obtained. The LOQ values are below the maximum residue levels (MRLs) established by European Regulation for grapes, with the exception of methidathion. Coefficients of correlation (R2) higher than 0.99 were obtained for the majority of the pesticides, in all different wines analyzed.

Determination of 24 pesticide residues in fortified wines by solid-phase microextraction and gas chromatography tandem mass spectrometry

The present work describes a solid-phase microextraction (SPME) gas chromatography_tandem mass spectrometry (MS/MS) method to quantify 24 pesticides in fortified white wine and fortified red wine. In this study “fortified wine” refers to a wine in which fermentation is arrested before completion by alcohol distillate addition, allowing sugar and alcoholic contents to be higher (around 80-100 g/L total sugars and 19-22% alcohol strength (v/v)). The analytical method showed good linearity, presenting correlation coefficients (R2) ≥ 0.989 for all compounds. Limits of detection (LOD) and quantitation (LOQ) in the ranges of 0.05-72.35 and 0.16-219.23 μg/L, respectively, were obtained. LOQs are below the maximum residue levels (MRL) set by European Regulation for grapes. The proposed method was applied to 17 commercial fortified wines. The analyzed pesticides were not detected in the wines tested.

Analysis of PCBs in soils and sediments by microwave-assisted extraction, headspace-SPME and high resolution gas chromatography with ion-trap tandem mass spectrometry

A procedure for the determination of seven indicator PCBs in soils and sediments using microwave-assisted extraction (MAE) and headspace solid-phase microextraction (HS-SPME) prior to GC-MS/MS is described. Optimization of the HS-SPME was carried out for the most important parameters such as extraction time, sample volume and temperature. The adopted methodology has reduced consumption of organic solvents and analysis runtime. Under the optimized conditions, the method detection limit ranged from 0.6 to 1 ng/g when 5 g of sample was extracted, the precision on real samples ranged from 4 to 21% and the recovery from 69 to 104%. The proposed method, which included the analysis of a certified reference material in its validation procedure, can be extended to several other PCBs and used in the monitoring of soil or sediments for the presence of PCBs.

Quantification of endocrine disruptors and pesticides in water by gas chromatography–tandem mass spectrometry. Method validation using weighted linear regression schemes

Amulti-residue methodology based on a solid phase extraction followed by gas chromatography–tandem mass spectrometry was developed for trace analysis of 32 compounds in water matrices, including estrogens and several pesticides from different chemical families, some of them with endocrine disrupting properties. Matrix standard calibration solutions were prepared by adding known amounts of the analytes to a residue-free sample to compensate matrix-induced chromatographic response enhancement observed for certain pesticides. Validation was done mainly according to the International Conference on Harmonisation recommendations, as well as some European and American validation guidelines with specifications for pesticides analysis and/or GC–MS methodology. As the assumption of homoscedasticity was not met for analytical data, weighted least squares linear regression procedure was applied as a simple and effective way to counteract the greater influence of the greater concentrations on the fitted regression line, improving accuracy at the lower end of the calibration curve. The method was considered validated for 31 compounds after consistent evaluation of the key analytical parameters: specificity, linearity, limit of detection and quantification, range, precision, accuracy, extraction efficiency, stability and robustness.

Enantiomeric fraction evaluation of pharmaceuticals in environmentalmatrices by liquid chromatography-tandem mass spectrometry

The interest for environmental fate assessment of chiral pharmaceuticals is increasing and enantioselective analytical methods are mandatory. This study presents an enantioselective analytical method for the quantification of seven pairs of enantiomers of pharmaceuticals and a pair of a metabolite. The selected chiral pharmaceuticals belong to three different therapeutic classes, namely selective serotonin reuptake inhibitors (venlafaxine, fluoxetine and its metabolite norfluoxetine), beta-blockers (alprenolol, bisoprolol, metoprolol, propranolol) and a beta2-adrenergic agonist (salbutamol). The analytical method was based on solid phase extraction followed by liquid chromatography tandem mass spectrometry with a triple quadrupole analyser. Briefly, Oasis® MCX cartridges were used to preconcentrate 250 mL of water samples and the reconstituted extracts were analysed with a Chirobiotic™ V under reversed mode. The effluent of a laboratory-scale aerobic granular sludge sequencing batch reactor (AGS-SBR) was used to validate the method. Linearity (r2 > 0.99), selectivity and sensitivity were achieved in the range of 20–400 ng L−1 for all enantiomers, except for norfluoxetine enantiomers which range covered 30–400 ng L−1. The method detection limits were between 0.65 and 11.5 ng L−1 and the method quantification limits were between 1.98 and 19.7 ng L−1. The identity of all enantiomers was confirmed using two MS/MS transitions and its ion ratios, according to European Commission Decision 2002/657/EC. This method was successfully applied to evaluate effluents of wastewater treatment plants (WWTP) in Portugal. Venlafaxine and fluoxetine were quantified as non-racemic mixtures (enantiomeric fraction ≠ 0.5). The enantioselective validated method was able to monitor chiral pharmaceuticals in WWTP effluents and has potential to assess the enantioselective biodegradation in bioreactors. Further application in environmental matrices as surface and estuarine waters can be exploited.

Milk intake is inversely related to body mass index and body fat in girls

Dairy foods comprise a range of products with varying nutritional content. The intake of dairy products (DPs) has been shown to have beneficial effects on body weight and body fat. This study aimed to examine the independent association between DP intake, body mass index (BMI), and percentage body fat (%BF) in adolescents. A cross-sectional, school-based study was conducted with 1,001 adolescents (418 boys), ages 15–18 years, from the Azorean Archipelago, Portugal. Anthropometric measurements were recorded (weight and height), and %BF was assessed using bioelectric impedance analysis. Adolescent food intake was measured using a self-administered, semiquantitative food frequency questionnaire. Data were analyzed separately for girls and boys, and separate multiple linear regression analysis was used to estimate the association between total DP, milk, yogurt, and cheese intake, BMI, and %BF, adjusting for potential confounders. For boys and girls, respectively, total DP consumption was 2.6 ± 1.9 and 2.9 ± 2.5 servings/day (P = 0.004), while milk consumption was 1.7 ± 1.4 and 2.0 ± 1.7 servings/day (P = 0.001), yogurt consumption was 0.5 ± 0.6 and 0.4 ± 0.7 servings/day (P = 0.247), and cheese consumption was 0.4 ± 0.6 and 0.5 ± 0.8 servings/day (P = 0.081). After adjusting for age, birth weight, energy intake, protein, total fat, sugar, dietary fiber, total calcium intake, low-energy reporters, parental education, pubertal stage, and physical activity, only milk intake was negatively associated with BMI and %BF in girls (respectively, girls: β = −0.167, P = 0.013; boys: β = −0.019, P = 0.824 and girls: β = −0.143, P = 0.030; boys: β = −0.051, P = 0.548). Conclusion: We found an inverse association between milk intake and both BMI and %BF only in girls.

CDIO and the European Project Semester: a match for capstone projects?

The CDIO Initiative is an open innovative educational framework for engineering graduation degrees set in the context of Conceiving – Designing – Implementing – Operating real-world systems and products, which is embraced by a network of worldwide universities, the CDIO collaborators. A CDIO compliant engineering degree programme typically includes a capstone module on the final semester. Its purpose is to expose students to problems of a greater dimension and complexity than those faced throughout the degree programme as well as to put them in contact with the so-called real world, in opposition to the academic world. However, even in the CDIO context, there are barriers that separate engineering capstone students from the real world context of an engineering professional: (i) limited interaction with experts from diverse scientific areas; (ii) reduced cultural and scientific diversity within the teams; and (iii) lack of a project supportive framework to foster the complementary technical and non-technical skills required in an engineering professional. To address these shortcomings, we propose the adoption of the European Project Semester (EPS) framework, a one semester student centred international capstone programme offered by a group of European engineering schools (the EPS Providers) as part of their student exchange programme portfolio. The EPS package is organised around a central module – the EPS project – and a set of complementary supportive modules. Project proposals refer to open multidisciplinary real world problems and supervision becomes coaching. The students are organised in teams, grouping individuals from diverse academic backgrounds and nationalities, and each team is fully responsible for conducting its project. EPS complies with the CDIO directives on Design-Implement experiences and provides an integrated framework for undertaking capstone projects, which is focussed on multicultural and multidisciplinary teamwork, problem-solving, communication, creativity, leadership, entrepreneurship, ethical reasoning and global contextual analysis. As a result, we recommend the adoption of the EPS within CDIO capstone modules for the benefit of engineering students.

Massive Open Online Course management: learning science and engineering through peer-reviewed projects

Massive Open Online Courses (MOOC) are gaining prominence in transversal teaching-learning strategies. However, there are many issues still debated, namely assessment, recognized largely as a cornerstone in Education. The large number of students involved requires a redefinition of strategies that often use approaches based on tasks or challenging projects. In these conditions and due to this approach, assessment is made through peer-reviewed assignments and quizzes online. The peer-reviewed assignments are often based upon sample answers or topics, which guide the student in the task of evaluating peers. This chapter analyzes the grading and evaluation in MOOCs, especially in science and engineering courses, within the context of education and grading methodologies and discusses possible perspectives to pursue grading quality in massive e-learning courses.

Interpretative research in information systems: two qualitative research design projects

In a scientific research project is important to define the underlying philosophical orientation of the project, because this will influence the choices made in respect of scientific methods used, as well as the way they will be applied. It is crucial, therefore, that the philosophy and research design strategy are consistent with each other. These questions become even more relevant in qualitative research. Historically, the interpretive research philosophy is more associated to the scientific areas of social sciences and humanities where the subjectivity inherent to human intervention is more explicitly defined. Information systems field are, primarily, trapped in computer science field, though it also integrates issues related with management and organizations field. This shift from a purely technological guidance for the consideration of the problems of management and organizations has fostered the rise of research projects according to the interpretive philosophy and using qualitative methods. This paper explores the importance of alignment between the epistemological orientation and research design strategy, in qualitative research projects. As a result, it is presented two PhD projects, with different research design strategies, that are being developed in the technology and information systems field, in the light of the interpretive paradigm.