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.

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.

A Manipulação de resultados em Portugal através do Goodwill

Dissertação para obtenção do Grau de Mestre em Contabilidade e Finanças Orientador: Doutor José Manuel da Veiga Pereira

Long-term price range forecast applied to risk management using regression models

Long-term contractual decisions are the basis of an efficient risk management. However those types of decisions have to be supported with a robust price forecast methodology. This paper reports a different approach for long-term price forecast which tries to give answers to that need. Making use of regression models, the proposed methodology has as main objective to find the maximum and a minimum Market Clearing Price (MCP) for a specific programming period, and with a desired confidence level α. Due to the problem complexity, the meta-heuristic Particle Swarm Optimization (PSO) was used to find the best regression parameters and the results compared with the obtained by using a Genetic Algorithm (GA). To validate these models, results from realistic data are presented and discussed in detail.

Peer Instruction method in introductory math courses

Learning is not a spectator’s sport. Students do not learn much by just sitting in class listening their teachers, memorizing pre-packaged assignments and spitting out answers. The teaching-learning process has been a constant target of studies, particularly in Higher Education, in consequence of the annual increase of new students. The concern with maintaining a desired quality level in the training of these students, conjugated with the will to widen the access to all of those who finish Secondary School Education, has triggered a greater intervention from the education specialists, in partnership with the teachers of all Higher Education areas, in the analysis of this problem. Considering the particular case of Engineering, it has been witnessed a rising concern with the active learning strategies and forms of assessment. Research has demonstrated that students learn more if they are actively engaged with the material they are studying. In this presentation we describe, present and discuss the techniques and the results of Peer Instruction method in an introductory Calculus courses of an Engineering Bach

Scheduling maintenance activities of electric power transmission networks using an hybrid constraint method

In this paper we present a Constraint Logic Programming (CLP) based model, and hybrid solving method for the Scheduling of Maintenance Activities in the Power Transmission Network. The model distinguishes from others not only because of its completeness but also by the way it models and solves the Electric Constraints. Specifically we present a efficient filtering algorithm for the Electrical Constraints. Furthermore, the solving method improves the pure CLP methods efficiency by integrating a type of Local Search technique with CLP. To test the approach we compare the method results with another method using a 24 bus network, which considerers 42 tasks and 24 maintenance periods.

An efficient method for optimal location and sizing of fixed and switched shunt capacitors in large distribution systems

This paper proposes a computationally efficient methodology for the optimal location and sizing of static and switched shunt capacitors in large distribution systems. The problem is formulated as the maximization of the savings produced by the reduction in energy losses and the avoided costs due to investment deferral in the expansion of the network. The proposed method selects the nodes to be compensated, as well as the optimal capacitor ratings and their operational characteristics, i.e. fixed or switched. After an appropriate linearization, the optimization problem was formulated as a large-scale mixed-integer linear problem, suitable for being solved by means of a widespread commercial package. Results of the proposed optimizing method are compared with another recent methodology reported in the literature using two test cases: a 15-bus and a 33-bus distribution network. For the both cases tested, the proposed methodology delivers better solutions indicated by higher loss savings, which are achieved with lower amounts of capacitive compensation. The proposed method has also been applied for compensating to an actual large distribution network served by AES-Venezuela in the metropolitan area of Caracas. A convergence time of about 4 seconds after 22298 iterations demonstrates the ability of the proposed methodology for efficiently handling large-scale compensation problems.

Research on using the decision tree method in order to select the best alternative for the pharmacies supply

Introduction / Aims: Adopting the important decisions represents a specific task of the manager. An efficient manager takes these decisions during a sistematic process with well-defined elements, each with a precise order. In the pharmaceutical practice and business, in the supply process of the pharmacies, there are situations when the medicine distributors offer a certain discount, but require payment in a shorter period of time. In these cases, the analysis of the offer can be made with the help of the decision tree method, which permits identifying the decision offering the best possible result in a given situation. The aims of the research have been the analysis of the product offers of many different suppliers and the establishing of the most advantageous ways of pharmacy supplying. Material / Methods: There have been studied the general product offers of the following medical stores: A&G Med, Farmanord, Farmexim, Mediplus, Montero and Relad. In the case of medicine offers including a discount, the decision tree method has been applied in order to select the most advantageous offers. The Decision Tree is a management method used in taking the right decisions and it is generally used when one needs to evaluate the decisions that involve a series of stages. The tree diagram is used in order to look for the most efficient means to attain a specific goal. The decision trees are the most probabilistic methods, useful when adopting risk taking decisions. Results: The results of the analysis on the tree diagrams have indicated the fact that purchasing medicines with discount (1%, 10%, 15%) and payment in a shorter time interval (120 days) is more profitable than purchasing without a discount and payment in a longer time interval (160 days). Discussion / Conclusion: Depending on the results of the tree diagram analysis, the pharmacies would purchase from the selected suppliers. The research has shown that the decision tree method represents a valuable work instrument in choosing the best ways for supplying pharmacies and it is very useful to the specialists from the pharmaceutical field, pharmaceutical management, to medicine suppliers, pharmacy practitioners from the community pharmacies and especially to pharmacy managers, chief – pharmacists.

Bid definition method for electricity markets based on an adaptive multiagent system

Electricity markets are complex environments with very particular characteristics. MASCEM is a market simulator developed to allow deep studies of the interactions between the players that take part in the electricity market negotiations. This paper presents a new proposal for the definition of MASCEM players’ strategies to negotiate in the market. The proposed methodology is multiagent based, using reinforcement learning algorithms to provide players with the capabilities to perceive the changes in the environment, while adapting their bids formulation according to their needs, using a set of different techniques that are at their disposal. Each agent has the knowledge about a different method for defining a strategy for playing in the market, the main agent chooses the best among all those, and provides it to the market player that requests, to be used in the market. This paper also presents a methodology to manage the efficiency/effectiveness balance of this method, to guarantee that the degradation of the simulator processing times takes the correct measure.

A study on the authentication method for TAmI in ambient intelligence (secure group decision making toolkit)

It is difficult to get the decision about an opinion after many users get the meeting in same place. It used to spend too much time in order to find solve some problem because of the various opinions of each other. TAmI (Group Decision Making Toolkit) is the System to Group Decision in Ambient Intelligence [1]. This program was composed with IGATA [2], WebMeeting and the related Database system. But, because it is sent without any encryption in IP / Password, it can be opened to attacker. They can use the IP / Password to the bad purpose. As the result, although they make the wrong result, the joined member can’t know them. Therefore, in this paper, we studied the applying method of user’s authentication into TAmI.

Estratégias de oferta em leilões simétricos no âmbito dos mercados liberalizados de electricidade

Mestrado em Engenharia Electrotécnica – Sistemas Eléctricos de Energia

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.

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.