Aumento da resposta analítica por meio da otimização do sistema de injeção sem divisão de fluxo em cromatografia gasosa empregando a lei dos gases ideais

This paper reports the development of an easy, fast and effective procedure for the verification of the ideal gas law in splitless injection systems in order to improve the response. Results of a group of pesticides were used to demonstrate the suitability of the approach. The procedure helps establish experimental parameters through theoretical aspects. The improved instrumental response allowed extraction with lower sample volumes, the minimization of time and costs and the simplification of sample preparation.

Principais técnicas de preparo de amostra para a determinação de resíduos de agrotóxicos em água por cromatografia líquida com detecção por arranjo de diodos e por espectrometria de massas

The determination of pesticide residues in water samples by Liquid Chromatography require sample preparation for extraction and enrichment of the analytes with the minimization of interferences to achieve adequate detection limits. The Solid Phase Extraction (SPE), Solid Phase Microextraction (SPME), Stir Bar Sorptive Extraction (SBSE) and Dispersive Liquid-Liquid Microextraction (DLLME) techniques have been widely used for extraction of pesticides in water. In this review, the principles of these sample preparation techniques associated with the analysis by Liquid Chromatography with Diode Array Detection (LC-DAD) or Mass Spectrometry (LC-MS) are described and an overview of several applications were presented and discussed.

Un método para enseñar el porqué suceden las reacciones químicas

A methodology is proposed for explaining one of the central questions in the teaching of general chemistry courses to freshman students: why do chemical transformations occur? The answer to this question is based on thermodynamics but we propose arriving at an answer in a more intuitive way by using computational tools in a bid to increase the motivation of students for learning chemistry.

Determinação de resíduos de agrotóxicos em leite bovino empregando método QuEChERS modificado e GC-MS/MS

Considering the possibility that pesticides used in cattle raising produce residues in milk and cause harm to public health, this study developed a multiresidue method for determination of pesticide residues in bovine milk, using a modified QuEChERS method for sample preparation, and quantification by GC-MS/MS. The method proved to be efficient, resulting in satisfactory recoveries in the range 71.1 to 117.4%, for 45 of the 48 compounds analyzed with RSD values < 17.3%. The method LOD and LOQ were3.0 and 10.0 µg L-1, respectively, except for cyfluthrin which showed 7.5 and 25.0 µg L-1.

Kunnallisen tai seudullisen toimitilahallinnon yhtiöittämisen edut ja haitat

Tutkimuksen aihe liittyy kunnallisten toimitilojen yhtiöittämiskysymykseen, joka on ollut esillä monissa kunnissa useita vuosia ja laajentunut nyt seudulliseksi. Tutkimuksen tavoitteena on tarkastella, mitä hyötyä tai haittaa kunnallisen tai seudullisen toimitilahallinnosta vastaavan yksikön yhtiöittämisestä olisi. Parantaakseen tuottavuutta kunta voi järjestää toimintansa perinteisen kunnallisen organisoinnin sijaan liikelaitoksena tai osakeyhtiönä silloin, kun toiminnan laatu on liiketoiminnan luonteista. Suurin osa kuntien toimitilakiinteistöistä toimii kuntien palvelutuotannon suoranaisena tuotantovälineenä. Kuntien välisen yhteistoiminnan lisääminen voidaan nähdä mahdollisuutena julkisella sektorilla. Sen lisääminen edesauttaa tuottavuuden kasvua ja mahdollistaa palvelujen jatkuvan kehittämisen. Yhtiöittäminen tuo toimintaan mukaan asioita, jotka varmasti tehostavat toimintaa, kuten päätöksenteon nopeutuminen, toiminnan joustavuus, joustava ja kilpailukykyinen henkilöstöhallinto sekä yhtiön toiminnan ja päätösten ei-julkisuus jne. Huonoja puolia yhtiöittämisessä on kuntien kiinteistömenojen mahdollinen nousu käyttötalouspuolella sekä se, että yhtiöllä olisi käytännössä vain muutama asiakas. Suomessa kuntien toimitilahallinto on todennäköisesti menossa kohti yhtiömallia. Vaihtoehtoina yhtiöittämiselle ovat siis liikelaitosmallin kehittäminen ja joissain tapauksissa keskinäinen kiinteistöyhtiömalli. Joka tapauksessa kuntien toimitilahallintoyksiköiden toimintaa ja toimintamallia pitää kehittää, jotta niiden tuottavuus kasvaa sekä toiminta säilyy kannattavana ja järkevänä. Ulkoisten tekijöiden vaikutus kuntien toimitilahallinnon toimintaan kasvaa koko ajan.

Utilization of a Time Domain Simulator in the Technical and Economic Analysis of a Wind Turbine Electric Drive Train

The amount of installed wind power has been growing exponentially during the past ten years. As wind turbines have become a significant source of electrical energy, the interactions between the turbines and the electric power network need to be studied more thoroughly than before. Especially, the behavior of the turbines in fault situations is of prime importance; simply disconnecting all wind turbines from the network during a voltage drop is no longer acceptable, since this would contribute to a total network collapse. These requirements have been a contributor to the increased role of simulations in the study and design of the electric drive train of a wind turbine. When planning a wind power investment, the selection of the site and the turbine are crucial for the economic feasibility of the installation. Economic feasibility, on the other hand, is the factor that determines whether or not investment in wind power will continue, contributing to green electricity production and reduction of emissions. In the selection of the installation site and the turbine (siting and site matching), the properties of the electric drive train of the planned turbine have so far been generally not been taken into account. Additionally, although the loss minimization of some of the individual components of the drive train has been studied, the drive train as a whole has received less attention. Furthermore, as a wind turbine will typically operate at a power level lower than the nominal most of the time, efficiency analysis in the nominal operating point is not sufficient. This doctoral dissertation attempts to combine the two aforementioned areas of interest by studying the applicability of time domain simulations in the analysis of the economicfeasibility of a wind turbine. The utilization of a general-purpose time domain simulator, otherwise applied to the study of network interactions and control systems, in the economic analysis of the wind energy conversion system is studied. The main benefits of the simulation-based method over traditional methods based on analytic calculation of losses include the ability to reuse and recombine existing models, the ability to analyze interactions between the components and subsystems in the electric drive train (something which is impossible when considering different subsystems as independent blocks, as is commonly done in theanalytical calculation of efficiencies), the ability to analyze in a rather straightforward manner the effect of selections other than physical components, for example control algorithms, and the ability to verify assumptions of the effects of a particular design change on the efficiency of the whole system. Based on the work, it can be concluded that differences between two configurations can be seen in the economic performance with only minor modifications to the simulation models used in the network interaction and control method study. This eliminates the need ofdeveloping analytic expressions for losses and enables the study of the system as a whole instead of modeling it as series connection of independent blocks with no lossinterdependencies. Three example cases (site matching, component selection, control principle selection) are provided to illustrate the usage of the approach and analyze its performance.

Personality and Depression

The aim of this study was to illustrate the associations of personality variables and depression. The first study population consisted of 50 patients with DSM-IV defined major depressive disorder. Subjects were randomized to receive either fluoxetine medication or short-term psychodynamic psychotherapy. The Hamilton Depression Rating Scale was completed at the baseline and in the follow-up at four months. Baseline mature defense style measured with the Defense Style Questionnaire predicted favourable outcome in the fluoxetine treatment group, whereas no associations were found in psychotherapy group. The Psychological Mindedness Scale scores were not predictive for recovery in patients receiving psychotherapy or medication. The Psychological Mindedness Scale seems not to be useful in selecting optimal treatment in major depressive disorder. Harm Avoidance measured with the Temperament and Character Inventory associated with the baseline severity of the depressive state. In the fluoxetine treatment group high Reward Dependence, high Self-Directedness and high Cooperativeness were predictive for more severe depression in the four months follow-up, whereas no associations were found in the psychotherapy treatment group. It is possible that the result reflects the differences in the placebo response. The second data were derived from the Finnish Public Sector Study. These prospective studies with four years follow-up focused on the predictive value of optimism and pessimism, first, to work disability with a diagnosis of depression lasting at least 90 days and returning to work (N= 38214) , and second, to the likelihood of initiating antidepressant medication treatment lasting at least 100 days and ending the treatment (N= 29930). Results show that low optimism associates with the elevated risk of work disability and higher likelihood of antidepressant use. High pessimism associated with higher likelihood starting at least 100 days antidepressant medication and not stopping medication during the follow up. High pessimism did not seem to predict the entering to depression related work disability, but in the case of disability period it associated with the lower likelihood of returning to work. The thesis shows that personality features play a role as a vulnerability factor, and influence the onset and course of depression. Taking these factors into account more than is currently done may increase the possibilities to enhance the treatment results in depression.

Hitsauksen aiheuttamat muodonmuutokset ja niiden hallinta alumiiniveneiden rakenteissa

Alumiiniveneissä hitsauksen aiheuttamat muodonmuutokset ovat usein erittäin haitallisia, koska niiden aiheuttamat mittamuutokset ja ulkonäölliset haitat alentavat tuotteen laatua sekä arvoa. Monissa tapauksissa myös hitsausliitoksen suorituskyky heikentyy ja lisäksi hitsausmuodonmuutokset voivat aiheuttaa toiminnallisia ongelmia alumiiniveneiden runkorakenteisiin. Tästä johtuen hitsausmuodonmuutosten hallinta ja minimointi ovat erityisen tärkeitä tekijöitä pyrittäessä parantamaan alumiiniveneiden laatua ja kustannustehokkuutta sekä kasvattamaan alumiinivenealan kilpailukykyä. Tässä diplomityössä tutkittiin robotisoidun kaasukaarihitsauksen aiheuttamia muodonmuutoksia sekä niiden hallintaa alumiinista valmistettujen työ- ja huviveneiden runkorakenteissa. Työssä perehdyttiin nykyaikaiseen alumiinivenevalmistukseen sekä hitsattujen rakenteiden yleisiin lujuusopin teorioihin ja käyttäytymismalleihin. Alumiinin hitsausmuodonmuutosten tutkimuksissa suoritettiin käytännön hitsauskokeita, joiden kohteina olivat alumiiniveneissä käytetyt rakenneratkaisut ja liitostyypit. Työn tavoitteena oli määrittää alumiinin hitsauksessa syntyviin muodonmuutoksiin keskeisesti vaikuttavia tekijöitä ja parametreja. Tutkimustulosten perusteella pyrittiin esittämään ratkaisuja alumiiniveneiden rakenteisiin aiheutuvien hitsausmuodonmuutosten vähentämiseksi ja hallitsemiseksi. Alumiinirakenteissa hitsausmuodonmuutokset ovat hyvin tapauskohtaisia, koska usein niiden syntyminen määräytyy monen tekijän yhteisvaikutuksesta. Teräsrakenteille käytetyt yleiset analyyttiset laskentakaavat ja käyttäytymismallit eivät sovellu suoraan alumiinirakenteille, mikä johtuu alumiinin erilaisista materiaaliominaisuuksista ja käyttäytymisestä hitsauksen aikana. Tulevaisuudessa empiiristen koejärjestelyiden ja analyyttisten mallien lisäksi sovellettavan numeerisen elementtimenetelmän avulla voidaan parantaa alumiinin hitsauksessa aiheutuvien muodonmuutosten kokonaisvaltaista hallintaa.

MCMC Analysis for Optimization of Stochastic Models

In any decision making under uncertainties, the goal is mostly to minimize the expected cost. The minimization of cost under uncertainties is usually done by optimization. For simple models, the optimization can easily be done using deterministic methods.However, many models practically contain some complex and varying parameters that can not easily be taken into account using usual deterministic methods of optimization. Thus, it is very important to look for other methods that can be used to get insight into such models. MCMC method is one of the practical methods that can be used for optimization of stochastic models under uncertainty. This method is based on simulation that provides a general methodology which can be applied in nonlinear and non-Gaussian state models. MCMC method is very important for practical applications because it is a uni ed estimation procedure which simultaneously estimates both parameters and state variables. MCMC computes the distribution of the state variables and parameters of the given data measurements. MCMC method is faster in terms of computing time when compared to other optimization methods. This thesis discusses the use of Markov chain Monte Carlo (MCMC) methods for optimization of Stochastic models under uncertainties .The thesis begins with a short discussion about Bayesian Inference, MCMC and Stochastic optimization methods. Then an example is given of how MCMC can be applied for maximizing production at a minimum cost in a chemical reaction process. It is observed that this method performs better in optimizing the given cost function with a very high certainty.

Computational modeling for irrigated agriculture planning. Part II: risk analysis

Techniques of evaluation of risks coming from inherent uncertainties to the agricultural activity should accompany planning studies. The risk analysis should be carried out by risk simulation using techniques as the Monte Carlo method. This study was carried out to develop a computer program so-called P-RISCO for the application of risky simulations on linear programming models, to apply to a case study, as well to test the results comparatively to the @RISK program. In the risk analysis it was observed that the average of the output variable total net present value, U, was considerably lower than the maximum U value obtained from the linear programming model. It was also verified that the enterprise will be front to expressive risk of shortage of water in the month of April, what doesn't happen for the cropping pattern obtained by the minimization of the irrigation requirement in the months of April in the four years. The scenario analysis indicated that the sale price of the passion fruit crop exercises expressive influence on the financial performance of the enterprise. In the comparative analysis it was verified the equivalence of P-RISCO and @RISK programs in the execution of the risk simulation for the considered scenario.

Broilers'toes asymmetry and walking ability assessment

Brazilian poultry production nowadays occupies important position in world's economy due to its technological advancement, which associated to the development of genetic strains of high growth may cause deviation in the growth rate and harm production. Morphological asymmetry has been pointed as an indicator of welfare, as maintained the pattern that leads to balance, the broiler chicken would have its normal locomotion characteristics, freely reaching water and feed. Thus, the objective of this research was to verify the possibility of using morphological asymmetry for evaluating walking ability of broiler chicken. The research was done in the Technology Center, at UNICAMP. The experiment was made using biomechanics analysis and following, the toes were measured. Results found did not show asymmetry useful for determining the locomotion ability of broiler chicken. New studies are recommended in order to search for other correlations that might help to estimate at field level, the locomotion difficulties of broiler chicken.

Development of capacitive sensor for measuring soil water content

The irrigation management based on the monitoring of the soil water content allows for the minimization of the amount of water applied, making its use more efficient. Taking into account these aspects, in this work, a sensor for measuring the soil water content was developed to allow real time automation of irrigation systems. This way, problems affecting crop yielding such as irregularities in the time to turn on or turn off the pump, and excess or deficit of water can be solved. To develop the sensors were used stainless steel rods, resin, and insulating varnish. The sensors measuring circuit was based on a microcontroller, which gives its output signal in the digital format. The sensors were calibrated using soil of the type “Quartzarenic Neosoil”. A third order polynomial model was fitted to the experimental data between the values of water content corresponding to the field capacity and the wilting point to correlate the soil water content obtained by the oven standard method with those measured by the electronic circuit, with a coefficient of determination of 93.17%, and an accuracy in the measures of ±0.010 kg kg-1. Based on the results, it was concluded that the sensor and its implemented measuring circuit can be used in the automation process of irrigation systems.

Spatial variability of air dry bulb temperature and black globe humidity index in a broiler house during the heating phase

The air dry-bulb temperature (t db),as well as the black globe humidity index (BGHI), exert great influence on the development of broiler chickens during their heating phase. Therefore, the aim of this study was to analyze the structure and the magnitude of the t db and BGHI spatial variability, using geostatistics tools such as semivariogram analysis and also producing kriging maps. The experiment was conducted in the west mesoregion of the states of Minas Gerais in 2010, in a commercial broiler house with heating system consisting of two furnaces that heat the air indirectly, in the firsts 14 days of the birds' life. The data were registered at intervals of five minutes in the period from 8 a.m. to 10 a.m. The variables were evaluated by variograms fitted by residual maximum likelihood (REML) testing the Spherical and Exponential models. Kriging maps were generated based on the best model used to fit the variogram. It was possible to characterize the variability of the t db and BGHI, which allowed observing the spatial dependence by using geostatistics techniques. In addition, the use of geostatistics and distribution maps made possible to identify problems in the heating system in regions inside the broiler house that may harm the development of chicks.

Redundant variables and the quality of management zones

ABSTRACT Precision agriculture (PA) allows farmers to identify and address variations in an agriculture field. Management zones (MZs) make PA more feasible and economical. The most important method for defining MZs is a fuzzy C-means algorithm, but selecting the variable for use as the input layer in the fuzzy process is problematic. BAZZI et al. (2013) used Moran’s bivariate spatial autocorrelation statistic to identify variables that are spatially correlated with yield while employing spatial autocorrelation. BAZZI et al. (2013) proposed that all redundant variables be eliminated and that the remaining variables would be considered appropriate on the MZ generation process. Thus, the objective of this work, a study case, was to test the hypothesis that redundant variables can harm the MZ delineation process. BAZZI This work was conducted in a 19.6-ha commercial field, and 15 MZ designs were generated by a fuzzy C-means algorithm and divided into two to five classes. Each design used a different composition of variables, including copper, silt, clay, and altitude. Some combinations of these variables produced superior MZs. None of the variable combinations produced statistically better performance that the MZ generated with no redundant variables. Thus, the other redundant variables can be discredited. The design with all variables did not provide a greater separation and organization of data among MZ classes and was not recommended.

The probabilistic risk analysis of external hazards of an interim storage for spent nuclear fuel

Tässä diplomityössä tehtiin Olkiluodon ydinvoimalaitoksella sijaitsevan käytetyn ydinpolttoaineen allasvarastointiin perustuvan välivaraston todennäköisyysperustainen ulkoisten uhkien riskianalyysi. Todennäköisyysperustainen riskianalyysi (PRA) on yleisesti käytetty riskien tunnistus- ja lähestymistapa ydinvoimalaitoksella. Työn tarkoituksena oli laatia täysin uusi ulkoisten uhkien PRA-analyysi, koska Suomessa ei ole aiemmin tehty vastaavanlaisia tämän tutkimusalueen riskitarkasteluja. Riskitarkastelun motiivina ovat myös maailmalla tapahtuneiden luonnonkatastrofien vuoksi korostunut ulkoisten uhkien rooli käytetyn ydinpolttoaineen välivarastoinnin turvallisuudessa. PRA analyysin rakenne pohjautui tutkimuksen alussa luotuun metodologiaan. Analyysi perustuu mahdollisten ulkoisten uhkien tunnistamiseen pois lukien ihmisen aikaansaamat tahalliset vahingot. Tunnistettujen ulkoisten uhkien esiintymistaajuuksien ja vahingoittamispotentiaalin perusteella ulkoiset uhat joko karsittiin pois tutkimuksessa määriteltyjen karsintakriteerien avulla tai analysoitiin tarkemmin. Tutkimustulosten perusteella voitiin todeta, että tiedot hyvin harvoin tapahtuvista ulkoisista uhista ovat epätäydellisiä. Suurinta osaa näistä hyvin harvoin tapahtuvista ulkoisista uhista ei ole koskaan esiintynyt eikä todennäköisesti koskaan tule esiintymään Olkiluodon vaikutusalueella tai edes Suomessa. Esimerkiksi salaman iskujen ja öljyaltistuksen roolit ja vaikutukset erilaisten komponenttien käytettävyyteen ovat epävarmasti tunnettuja. Tutkimuksen tuloksia voidaan pitää kokonaisuudessaan merkittävinä, koska niiden perusteella voidaan osoittaa ne ulkoiset uhat, joiden vaikutuksia olisi syytä tutkia tarkemmin. Yksityiskohtaisempi tietoisuus hyvin harvoin esiintyvistä ulkoisista uhista tarkentaisi alkutapahtumataajuuksien estimaatteja.