Análise de agrotóxicos em água usando extração líquido-líquido com partição em baixa temperatura por cromatografia líquida de alta eficiência

This study optimized and validated the liquid-liquid extraction technique with partition at low temperature (LLE-PLT) for identification and quantification of four pesticides (chlorpyrifos, λ-cyhalothrin, permethrin, bifenthrin) in water samples. Analyses were performed by HPLC-UV. The technique was efficient for pesticide recovery with extraction exceeding 86%. Chromatographic response was linear for the four compounds in the 10-45 µg L-1 range, with correlation coefficients greater than 0.99. Limits of detection and quantitation were less than 3.5 µg L-1 and equal to 10 µg L-1, respectively. The proposed method was applied to 29 water samples from the Jaíba Project in northern Minas Gerais.

Otimização e validação da extração sólido-líquido e purificação em baixa temperatura de HPAs em lodo de esgoto

In this study, a method of solid-liquid extraction and purification at low temperature (SLE-PLT) to determine 16 polycyclic aromatic hydrocarbons (PAHs) in sewage sludge was optimized and validated. The analyses were performed by HPLC-UV. The extraction phase, homogenization procedure, influence of pH, ionic strength and clean-up of the extracts were optimized. Recoveries were higher than 63.4% for 11 PAHs. The correlation coefficients were greater than 0.99 and limits of detection and quantitation were less than 0.060 and 0.15 µg g-1, respectively. These values were lower than the maximum residue limits of PAHs established by European legislation. SLE-PLT proved a more practical, economical method with fewer steps compared to Soxhlet extraction (reference method) for PAHs in sewage sludge.

Determination of triamterene in human plasma and urine after its cloud point extraction

A new analytical approach was developed involving cloud point extraction (CPE) and spectrofluorimetric determination of triamterene (TM) in biological fluids. A urine or plasma sample was prepared and adjusted to pH 7, then TM was quickly extracted using CPE, using 0.05% (w/v) of Triton X-114 as the extractant. The main factors that affected the extraction efficiency (the pH of the sample, the Triton X-114 concentration, the addition of salt, the extraction time and temperature, and the centrifugation time and speed) were studied and optimized. The method gave calibration curves for TM with good linearities and correlation coefficients (r) higher than 0.99. The method showed good precision and accuracy, with intra- and inter-assay precisions of less than 8.50% at all concentrations. Standard addition recovery tests were carried out, and the recoveries ranged from 94.7% to 114%. The limits of detection and quantification were 3.90 and 11.7 µg L-1, respectively, for urine and 5.80 and 18.0 µg L-1, respectively, for plasma. The newly developed, environmentally friendly method was successfully used to extract and determine TM in human urine samples.

Effect of temperature, leaf wetness, and rainfall on the production of Guignardia citricarpa ascospores and on back spot severity on sweet orange

The black spot of citrus (Citrus sp.) is caused by Guignardia citricarpa with ascospore production depending on temperature, leaf wetness, and rainfall. The number of ascospores produced was monitored using a spore trap and climatic factors were recorded using an automated meteorological station of 'Natal' and 'Valencia' sweet orange (Citrus sinensis) orchards in Mogi Guaçu in the state of São Paulo, Brazil, from November 2000 to March 2001. The fruits were bagged to prevent infection and the bags removed from different sets of fruit for one week during each of the 18 weeks of the season in both orchards. Ascospores were produced during the entire experimental period, from spring through summer, primarily after rain events. In both orchards, ascospore production reached a peak in January and February. Ascospore production was related to leaf wetness only in the Natal orange orchard but was not related to total rainfall or temperature in either orchard. Disease was most severe on fruit exposed the 7th, 8th, and 13th weeks after beginning the experiment in both cultivars as well as after the 16th week for 'Natal'. There was a strong relationship between disease severity and total rainfall for both orchards and a weak correlation between temperature and severity in the 'Natal' block only. There was no relationship between severity and leaf wetness or ascospore numbers.

Evaluation of group electronegativities and hardness (softness) of group 14 elements and containing functional groups through density functional theory and correlation with NMR spectra data

Quantum Chemical calculations for group 14 elements of Periodic Table (C, Si, Ge, Sn, Pb) and their functional groups have been carried out using Density Functional Theory (DFT) based reactivity descriptors such as group electronegativities, hardness and softness. DFT calculations were performed for a large series of tetracoordinated Sn compounds of the CH3SnRR'X type, where X is a halogen and R and R' are alkyl, halogenated alkyl, alkoxy, or alkyl thio groups. The results were interpreted in terms of calculated electronegativity and hardness of the SnRR'X groups, applying a methodology previously developed by Geerlings and coworkers (J. Phys. Chem. 1993, 97, 1826). These calculations allowed to see the regularities concerning the influence of the nature of organic groups RR' and inorganic group X on electronegativities and hardness of the SnRR'X groups; in this case, it was found a very good correlation between the electronegativity of the fragment and experimental 119Sn chemical shifts, a property that sensitively reflects the change in the valence electronic structure of molecules. This work was complemented with the study of some compounds of the EX and ER types, where E= C, Si, Ge, Sn and R= CH3, H, which was performed to study the influence that the central atom has on the electronegativity and hardness of molecules, or whether these properties are mainly affected for the type of ligand bound to the central atom. All these calculations were performed using the B3PW91 functional together with the 6-311++G** basis set level for H, C, Si, Ge, F, Cl and Br atoms and the 3-21G for Sn and I atoms.

On the development of object functions and restrictions for shapes made with a turret punch press

This study presents the information required to describe the machine and device resources in the turret punch press environment which are needed for the development of the analysing method for automated production. The description of product and device resources and their interconnectedness is the starting point for method comparison the development of expenses, production planning and the performance of optimisation. The manufacturing method cannot be optimized unless the variables and their interdependence are known. Sheet metal parts in particular may then become remarkably complex, and their automatic manufacture may be difficult or, with some automatic equipment, even impossible if not know manufacturing properties. This thesis consists of three main elements, which constitute the triangulation. In the first phase of triangulation, the manufacture occuring on a turret punch press is examined in order to find the factors that affect the efficiency of production. In the second phase of triangulation, the manufacturability of products on turret punch presses is examined through a set of laboratory tests. The third phase oftriangulation involves an examination of five industry parts. The main key findings of this study are: all possible efficiency in high automation level machining cannot be achieved unless the raw materials used in production and the dependencies of the machine and tools are well known. Machine-specific manufacturability factors for turret punch presses were not taken into account in the industrial case samples. On the grounds of the performed tests and industrial case samples, the designer of a sheet metal product can directly influence the machining time, material loss, energy consumption and the number of tools required on a turret punch press by making decisions in the way presented in the hypothesis of thisstudy. The sheet metal parts to be produced can be optimised to bemanufactured on a turret punch press when the material to be used and the kinds of machine and tool options available are known. This provides in-depth knowledge of the machine and tool properties machine and tool-specifically. None of the optimisation starting points described here is a separate entity; instead, they are all connected to each other.

Determination of sugars and organic acids in pulp samples by capillary electrophoresis with UV detection

This MSc work was done in the project of BIOMECON financed by Tekes. The prime target of the research was, to develop methods for separation and determination of carbohydrates (sugars), sugar acids and alcohols, and some other organic acids in hydrolyzed pulp samples by capillary electrophoresis (CE) using UV detection. Aspen, spruce, and birch pulps are commonly used for production of papers in Finland. Feedstock components in pulp predominantly consist of carbohydrates, organic acids, lignin, extractives, and proteins. Here in this study, pulps have been hydrolyzed in analytical chemistry laboratories of UPM Company and Lappeenranta University in order to convert them into sugars, acids, alcohols, and organic acids. Foremost objective of this study was to quantify and identify the main and by-products in the pulp samples. For the method development and optimization, increased precision in capillary electrophoresis was accomplished by calculating calibration data of 16 analytes such as D-(-)-fructose, D(+)-xylose, D(+)-mannose, D(+)-cellobiose, D-(+)-glucose, D-(+)-raffinose, D(-)-mannitol, sorbitol, rhamnose, sucrose, xylitol, galactose, maltose, arabinose, ribose, and, α-lactose monohydratesugars and 16 organic acids such as D-glucuronic, oxalic, acetic, propionic, formic, glycolic, malonic, maleic, citric, L-glutamic, tartaric, succinic, adipic, ascorbic, galacturonic, and glyoxylic acid. In carbohydrate and polyalcohol analyses, the experiments with CE coupled to direct UV detection and positive separation polarity was performed in 36 mM disodium hydrogen phosphate electrolyte solution. For acid analyses, CE coupled indirect UV detection, using negative polarity, and electrolyte solution made of 2,3 pyridinedicarboxylic acid, Ca2+ salt, Mg2+ salts, and myristyltrimethylammonium hydroxide in water was used. Under optimized conditions, limits of detection, relative standard deviations and correlation coefficients of each compound were measured. The optimized conditions were used for the identification and quantification of carbohydrates and acids produced by hydrolyses of pulp. The concentrations of the analytes varied between 1 mg – 0.138 g in liter hydrolysate.

Automated, adaptive methods for forest inventory

Forest inventories are used to estimate forest characteristics and the condition of forest for many different applications: operational tree logging for forest industry, forest health state estimation, carbon balance estimation, land-cover and land use analysis in order to avoid forest degradation etc. Recent inventory methods are strongly based on remote sensing data combined with field sample measurements, which are used to define estimates covering the whole area of interest. Remote sensing data from satellites, aerial photographs or aerial laser scannings are used, depending on the scale of inventory. To be applicable in operational use, forest inventory methods need to be easily adjusted to local conditions of the study area at hand. All the data handling and parameter tuning should be objective and automated as much as possible. The methods also need to be robust when applied to different forest types. Since there generally are no extensive direct physical models connecting the remote sensing data from different sources to the forest parameters that are estimated, mathematical estimation models are of "black-box" type, connecting the independent auxiliary data to dependent response data with linear or nonlinear arbitrary models. To avoid redundant complexity and over-fitting of the model, which is based on up to hundreds of possibly collinear variables extracted from the auxiliary data, variable selection is needed. To connect the auxiliary data to the inventory parameters that are estimated, field work must be performed. In larger study areas with dense forests, field work is expensive, and should therefore be minimized. To get cost-efficient inventories, field work could partly be replaced with information from formerly measured sites, databases. The work in this thesis is devoted to the development of automated, adaptive computation methods for aerial forest inventory. The mathematical model parameter definition steps are automated, and the cost-efficiency is improved by setting up a procedure that utilizes databases in the estimation of new area characteristics.

Automated Software Testing in Machine Automation

The problem of software (SW) defaults is becoming more and more topical because of increasing amount of the SW and its complication. The majority of these defaults are founded during the test part that consumes about 40-50% of the development efforts. Test automation allows reducing the cost of this process and increasing testing effectiveness. In the middle of 1980 the first tools for automated testing appeared and the automated process was implemented in different kinds of SW testing. In short time, it became obviously, automated testing can cause many problems such as increasing product cost, decreasing reliability and even project fail. This thesis describes automated testing process, its concept, lists main problems, and gives an algorithm for automated test tools selection. Also this work presents an overview of the main automated test tools for embedded systems.

Benefits of automated acclimatization during the pre-milking phase of lactating girolando cows

The aim of this paper was to evaluate the automated acclimatization effects during pre-milking of cows on thermal conditioning, physiology, milk production and cost-benefit of the automated adiabatic evaporative cooling system (AECS). The treatments 20; 30; 40 min and control consisted of exposure time of pre-milking cows to the automated AECS. Sixteen cows were used with an average daily milk yield of 19 kg, distributed in a 4 x 4 Latin square design. The Tukey's test (P<0.05) was used to compare the means. The environmental variables, dry bulb temperature (DBT, ºC) and relative humidity (RH, %), were recorded every minute, which allowed the determination of the system efficiency through the Temperature and Humidity Index (THI). The respiratory rate (RR), rectal temperature (RT) and temperature of the coat (TC) were measured before and after the acclimatization. The 40 min treatment kept the environmental variables and the comfort indexes within recommended limits. The physiological variables (RR, RT and TC) were lower in the 40 min treatment and reflected positively on milk production, which increased 3.66% compared to the control treatment. The system was profitable, having a 43 days return on investment and a monthly revenue increase of R$ 1,992.67.

Emerald zoyzia grass development regarding photosynthetically active radiation in different slopes

With this study, the objective was to estimate the photosynthetically active radiation (PAR) and to correlate it with the dry matter (MMSPA) of the emerald zoysia (Zoysia japonica Steud.) on surfaces with different expositions and slopes. The research was conducted at the Experimental Watershed of the Agricultural Engineering Department, School of Agriculture and Veterinary Sciences of São Paulo State University (FCAV/UNESP), Brazil, where the surfaces (H, 10 N, 30 N, 50 N, 10 S, 30 S, 50 S, 10 L, 30 L, 50 L, 10 O, 30 O and 50 O) were used. To obtain the global solar radiation, it was installed an automated weather station where the PAR (dependent variable) was obtained by the equation y = a + bx, and the global radiation was independent. To compare means of MMSPA, it was used the Tukey test at 5% probability, and to assess the relation PAR/MMSPA, the simple linear correlation coefficient. The result showed that the accumulation of these effects in the PAR increases with North exposure and decreases with the South, and exposure to 50N is most suitable for slopes, not having correlation between the PAR and the MMSPA for the surfaces evaluated for the study period.

Development of an automated bench top electronic penetrometer

The aim of this study was to develop a an automated bench top electronic penetrometer (ABEP) that allows performing tests with high rate of data acquisition (up to 19,600 Hz) and with variation of the displacement velocity and of the base area of cone penetration. The mechanical components of the ABEP are: a supporting structure, stepper motor, velocity reducer, double nut ball screw and six penetration probes. The electronic components of ABEP are: a "driver" to control rotation and displacement, power supply, three load cells, two software programs for running and storing data, and a data acquisition module. This penetrometer presented in compact size, portable and in 32 validation tests it proved easy to operate, and showed high resolution, high velocity in reliability in data collection. During the validation tests the equipment met the objectives, because the test results showed that the ABEP could use different sizes of cones, allowed work at different velocities, showed for velocity and displacement, were only 1.3% and 0.7%, respectively, at the highest velocity (30 mm s-1) and 1% and 0.9%, respectively for the lowest velocity (0.1 mm s-1).

Soybean yield maps using regular and optimized sample with different configurations by simulated annealing

ABSTRACT This study aimed to compare thematic maps of soybean yield for different sampling grids, using geostatistical methods (semivariance function and kriging). The analysis was performed with soybean yield data in t ha-1 in a commercial area with regular grids with distances between points of 25x25 m, 50x50 m, 75x75 m, 100x100 m, with 549, 188, 66 and 44 sampling points respectively; and data obtained by yield monitors. Optimized sampling schemes were also generated with the algorithm called Simulated Annealing, using maximization of the overall accuracy measure as a criterion for optimization. The results showed that sample size and sample density influenced the description of the spatial distribution of soybean yield. When the sample size was increased, there was an increased efficiency of thematic maps used to describe the spatial variability of soybean yield (higher values of accuracy indices and lower values for the sum of squared estimation error). In addition, more accurate maps were obtained, especially considering the optimized sample configurations with 188 and 549 sample points.

Voimalaitoksen käytönaikaisen optimoinnin määrittely

Tässä diplomityössä määritellään biopolttoainetta käyttävän voimalaitoksen käytönaikainen tuotannon optimointimenetelmä. Määrittelytyö liittyy MW Powerin MultiPower CHP –voimalaitoskonseptin jatkokehitysprojektiin. Erilaisten olemassa olevien optimointitapojen joukosta valitaan tarkoitukseen sopiva, laitosmalliin ja kustannusfunktioon perustuva menetelmä, jonka tulokset viedään automaatiojärjestelmään PID-säätimien asetusarvojen muodossa. Prosessin mittaustulosten avulla lasketaan laitoksen energia- ja massataseet, joiden tuloksia käytetään seuraavan optimointihetken lähtötietoina. Optimoinnin kohdefunktio on kustannusfunktio, jonka termit ovat voimalaitoksen käytöstä aiheutuvia tuottoja ja kustannuksia. Prosessia optimoidaan säätimille annetut raja-arvot huomioiden niin, että kokonaiskate maksimoituu. Kun laitokselle kertyy käyttöikää ja historiadataa, voidaan prosessin optimointia nopeuttaa hakemalla tilastollisesti historiadatasta nykytilanteen olosuhteita vastaava hetki. Kyseisen historian hetken katetta verrataan kustannusfunktion optimoinnista saatuun katteeseen. Paremman katteen antavan menetelmän laskemat asetusarvot otetaan käyttöön prosessin ohjausta varten. Mikäli kustannusfunktion laskenta eikä historiadatan perusteella tehty haku anna paranevaa katetta, niiden laskemia asetusarvoja ei oteta käyttöön. Sen sijaan optimia aletaan hakea deterministisellä optimointialgoritmilla, joka hakee nykyhetken ympäristöstä paremman katteen antavia säätimien asetusarvoja. Säätöjärjestelmä on mahdollista toteuttaa myös tulevaisuutta ennustavana. Työn käytännön osuudessa voimalaitosmalli luodaan kahden eri mallinnusohjelman avulla, joista toisella kuvataan kattilan ja toisella voimalaitosprosessin toimintaa. Mallinnuksen tuloksena saatuja prosessiarvoja hyödynnetään lähtötietoina käyttökatteen laskennassa. Kate lasketaan kustannusfunktion perusteella. Tuotoista suurimmat liittyvät sähkön ja lämmön myyntiin sekä tuotantotukeen, ja suurimmat kustannukset liittyvät investoinnin takaisinmaksuun ja polttoaineen ostoon. Kustannusfunktiolle tehdään herkkyystarkastelu, jossa seurataan katteen muutosta prosessin teknisiä arvoja muutettaessa. Tuloksia vertaillaan referenssivoimalaitoksella suoritettujen verifiointimittausten tuloksiin, ja havaitaan, että tulokset eivät ole täysin yhteneviä. Erot johtuvat sekä mallinnuksen puutteista että mittausten lyhyehköistä tarkasteluajoista. Automatisoidun optimointijärjestelmän käytännön toteutusta alustetaan määrittelemällä käyttöön otettava optimointitapa, siihen liittyvät säätöpiirit ja tarvittavat lähtötiedot. Projektia tullaan jatkamaan järjestelmän ohjelmoinnilla, testauksella ja virityksellä todellisessa voimalaitosympäristössä ja myöhemmin ennustavan säädön toteuttamisella.

A platform for anti-biofilm assays combining viability, biomass and matrix quantifications in susceptibility assessments of antimicrobials against Staphylococcus aureus biofilms

Bacteria can exist as planktonic, the lifestyle in which single cells exist in suspension, and as biofilms, which are surface-attached bacterial communities embedded in a selfproduced matrix. Most of the antibiotics and the methods for antimicrobial work have been developed for planktonic bacteria. However, the majority of the bacteria in natural habitats live as biofilms. Biofilms develop dauntingly fast high resistance towards conventional antibacterial treatments and thus, there is a great need to meet the demands of effective anti-biofilm therapy. In this thesis project it was attempted to fill the void of anti-biofilm screening methods by developing a platform of assays that evaluate the effect that screened compounds have on the total biomass, viability and the extracellular polysaccharide (EPS) layer of the biofilms. Additionally, a new method for studying biofilms and their interactions with compounds in a continuous flow system was developed using capillary electrochromatography (CEC). The screening platform was utilized with a screening campaign using a small library of cinchona alkaloids. The assays were optimized to be statistically robust enough for screening. The first assay, based on crystal violet staining, measures total biofilm biomass, and it was automated using a liquid handling workstation to decrease the manual workload and signal variation. The second assay, based on resazurin staining, measures viability of the biofilm, and it was thoroughly optimized for the strain used, but was then a very simple and fast method to be used for primary screening. The fluorescent resazurin probe is not toxic to the biofilms. In fact, it was also shown in this project that staining the biofilms with resazurin prior to staining with crystal violet had no effect on the latter and they can be used in sequence on the same screening plate. This sequential addition step was indeed a major improvement on the use of reagents and consumables and also shortened the work time. As a third assay in the platform a wheat germ agglutinin based assay was added to evaluate the effect a compound has on the EPS layer. Using this assay it was found that even if compounds might have clear effect on both biomass and viability, the EPS layer can be left untouched or even be increased. This is a clear implication of the importance of using several assays to be able to find “true hits” in a screening setting. In the pilot study of screening for antimicrobial and anti-biofilm effects using a cinchona alkaloid library, one compound was found to have antimicrobial effect against planktonic bacteria and prevent biofilm formation at low micromolar concentration. To eradicate biofilms, a higher concentration was needed. It was also shown that the chemical space occupied by the active compound was slightly different than the rest of the cinchona alkaloids as well as the rest of the compounds used for validatory screening during the optimization processes of the separate assays.