Reconhecimento de padrões por métodos não supervisionados: explorando procedimentos quimiométricos para tratamento de dados analíticos

An activity for introducing hierarchical cluster analysis (HCA) and principal component analysis (PCA) during the Instrumental Analytical Chemistry course is presented. The posed problem involves the discrimination of mineral water samples according to their geographical origin. Thirty-seven samples of 9 different brands were considered and the results from the determination of Na, K, Mg, Ca, Sr and Ba were taken into account. Non-supervised methods for pattern recognition were explored to construct a dendrogram, score and loading plots. The devised activity can be adopted for introducing Chemometrics devoted to data handling, stressing its importance in the context of modern Analytical Chemistry.

Workplace Social Capital and Employee Health

Työyhteisön sosiaalinen pääoma ja työntekijöiden terveys Monien tutkimusten mukaan sosiaalinen pääoma vaikuttaa terveyteen. Vaikka työssä käyvä väestönosa on merkittävän osan valveillaoloajastaan työyhteisössä, siellä kertyvää sosiaalista pääomaa on toistaiseksi tutkittu vähän. Tässä tutkimuksessa selvitettiin työyhteisön sosiaalisen pääoman ja kuntatyöntekijöiden terveyden välistä yhteyttä pitkittäisasetelmassa hyödyntäen Kuntasektorin henkilöstön seurantatutkimuksen aineistoa vuosilta 2000–2005. Yhteensä 48592 kuntatyöntekijää vastasi kyselyyn vuosina 2000–02 (vastausprosentti 68 %). Heistä 35914 (77 %) osallistui myös seurantatutkimukseen vuosina 2004–05. Tutkimuksessa kehitettiin kyselyyn perustuva työyhteisön sosiaalisen pääoman mittausmenetelmä. Työntekijän omaan arvioon perustuvan sosiaalisen pääoman lisäksi mitattiin työyhteisön sosiaalista pääomaa käyttämällä samassa työyhteisössä työskentelevien muiden työntekijöiden keskimääräistä arviota sosiaalisesta pääomasta. Terveyttä mitattiin kysymyksellä koetusta terveydestä. Masennusta arvioitiin sekä kysymällä lääkärin toteamasta masennuksesta että masennuslääkeostoilla Kelan lääkerekistereistä. Analyyseihin otettiin mukaan vain ne kuntatyöntekijät, jotka olivat lähtötilanteissa terveitä eli kokivat terveytensä hyväksi tai heillä ei ollut aiempaa diagnosoitua tai lääkehoitoa vaatinutta masennusta. Tulosten analysointiin käytettiin monitasomallinnusta. Tulokset vakioitiin sosiodemografisten tekijöiden ja terveyskäyttäytymisen suhteen. Neljän vuoden seurannassa sekä jatkuvasti vähäinen että vähenevä yksilön sosiaalinen pääoma työssä lisäsi riskiä koetun terveyden heikkenemiseen niillä kuntatyöntekijöillä, jotka eivät vaihtaneet työpaikkaa seurannan aikana ja jotka seurannan alussa kokivat terveytensä hyväksi. Tulos ei selittynyt sosiodemografisilla tekijöillä tai terveyskäyttäytymisen eroilla. Tuloksen merkittävyyttä tuki havainto, että myös työtoverien arvioon perustuva sosiaalinen pääoma ennusti oman terveyden huononemista seuranta-aikana. Niillä työntekijöillä, jotka työskentelivät sellaisissa työyhteisöissä, joissa koko seurannan ajan oli vähiten sosiaalista pääomaa, oli lähes 1.3 -kertainen riski terveyden heikentymiseen. Vähäinen omaan arvioon perustuva sosiaalinen pääoma työssä ennusti myös masennuksen ilmaantuvuutta lähtötilanteessa ei-masentuneilla lähes neljän vuoden seurannassa. Matalaan sosiaaliseen pääomaan liittyi 20–50 % suurempi todennäköisyys sairastua masennukseen seurannan aikana niin itseraportoidun lääkärin totea-man masennuksen kuin masennuslääkeostojen perusteella. Tätä tulosta ei kuitenkaan pystytty toistamaan käyttämällä oman arvion sijasta työtoverien arviota työyhteisön sosiaalisesta pääomasta. Tutkimusta sosiaalisen pääoman vaikutusta masennuksen ilmaantumiseen jatkettiin selvittämällä miten sosiaalisen pääoman eri ulottuvuudet vaikuttivat masennuksen ilmaantumiseen. Tulosten mukaan sosiaalisen pääoman vertikaalinen komponentti (työntekijöiden ja esimiesten välinen luottamus, vastavuoroisuus ja jaetut arvot ja normit, jotka edesauttavat yhteistyötä) sekä horisontaalinen komponentti (työntekijöiden välisissä suhteissa yhteistyöstä, luottamuksesta ja vastavuoroisuudesta syntyvä sosiaalinen pääoma) vaikuttivat itsenäisesti masennusriskiin. Tutkimuksen perusteella korkea työyhteisön sosiaalinen pääoma saattaa vaikuttaa edullisesti työntekijöiden terveyteen. Jos näin on, olisi tärkeää edistää työyhteisöjen sosiaalista pääomaa ja kannustaa sellaiseen toimintaan, joka lisää suvaitsevaisuutta, luottamusta ja vastavuoroisuutta sekä työntekijöiden kesken että työntekijöiden ja esimiesten välillä.

Utilização de zeólitas sintetizadas a partir de xisto retortado na remoção de arsênio em águas contaminadas

The solid by-product of the oil shale processing (PETROBRAS - Brazil) was used as raw material to synthesize zeolites A and faujasite. Alkaline fusion followed by hydrothermal treatment was the synthesis procedure used, and five different starting material compositions were obtained. The more crystalline zeolite-type materials synthesized, the pretreated oil shale ash and commercial zeolites were used as adsorbents in the purification of pollutant solutions with arsenic. The zeolite-type material composed of a mixture of zeolite A (42.6%) and faujasite (52.9%) presented an ion exchange capacity comparable to the pure zeolites A and faujasite, much better than the pretreated ash.

Análise multivariada de parâmetros físico-químicos em amostras de vinhos tintos comercializados na região metropolitana do Recife

The Brazilian legislation requires analysis of certain parameters to classify a wine and allow its commercialization. Some physico-chemical and some color parameters were determined in this work in samples of different red wines sold in the metropolitan area of Recife. Multivariate analysis comprising principal component analysis and hierarchical cluster analysis was employed to distinguish the analyzed wines. The results for pH, chloride concentration, color parameters and ammonium content were the most important variables for sample classification. It was also possible to classify the wines as soft or dry wines and amongst the soft wines we could determine two out of four winegrowing producers.

Conservation Genetics of Exploited Finnish Salmonid Fishes

Genetic diversity is one of the levels of biodiversity that the World Conservation Union (IUCN) has recognized as being important to preserve. This is because genetic diversity is fundamental to the future evolution and to the adaptive flexibility of a species to respond to the inherently dynamic nature of the natural world. Therefore, the key to maintaining biodiversity and healthy ecosystems is to identify, monitor and maintain locally-adapted populations, along with their unique gene pools, upon which future adaptation depends. Thus, conservation genetics deals with the genetic factors that affect extinction risk and the genetic management regimes required to minimize the risk. The conservation of exploited species, such as salmonid fishes, is particularly challenging due to the conflicts between different interest groups. In this thesis, I conduct a series of conservation genetic studies on primarily Finnish populations of two salmonid fish species (European grayling, Thymallus thymallus, and lake-run brown trout, Salmo trutta) which are popular recreational game fishes in Finland. The general aim of these studies was to apply and develop population genetic approaches to assist conservation and sustainable harvest of these populations. The approaches applied included: i) the characterization of population genetic structure at national and local scales; ii) the identification of management units and the prioritization of populations for conservation based on evolutionary forces shaping indigenous gene pools; iii) the detection of population declines and the testing of the assumptions underlying these tests; and iv) the evaluation of the contribution of natural populations to a mixed stock fishery. Based on microsatellite analyses, clear genetic structuring of exploited Finnish grayling and brown trout populations was detected at both national and local scales. Finnish grayling were clustered into three genetically distinct groups, corresponding to northern, Baltic and south-eastern geographic areas of Finland. The genetic differentiation among and within population groups of grayling ranged from moderate to high levels. Such strong genetic structuring combined with low genetic diversity strongly indicates that genetic drift plays a major role in the evolution of grayling populations. Further analyses of European grayling covering the majority of the species’ distribution range indicated a strong global footprint of population decline. Using a coalescent approach the beginning of population reduction was dated back to 1 000-10 000 years ago (ca. 200-2 000 generations). Forward simulations demonstrated that the bottleneck footprints measured using the M ratio can persist within small populations much longer than previously anticipated in the face of low levels of gene flow. In contrast to the M ratio, two alternative methods for genetic bottleneck detection identified recent bottlenecks in six grayling populations that warrant future monitoring. Consistent with the predominant role of random genetic drift, the effective population size (N_e) estimates of all grayling populations were very low with the majority of N_e estimates below 50. Taken together, highly structured local populations, limited gene flow and the small N_e of grayling populations indicates that grayling populations are vulnerable to overexploitation and, hence, monitoring and careful management using the precautionary principles is required not only in Finland but throughout Europe. Population genetic analyses of lake-run brown trout populations in the Inari basin (northernmost Finland) revealed hierarchical population structure where individual populations were clustered into three population groups largely corresponding to different geographic regions of the basin. Similar to my earlier work with European grayling, the genetic differentiation among and within population groups of lake-run brown trout was relatively high. Such strong differentiation indicated that the power to determine the relative contribution of populations in mixed fisheries should be relatively high. Consistent with these expectations, high accuracy and precision in mixed stock analysis (MSA) simulations were observed. Application of MSA to indigenous fish caught in the Inari basin identified altogether twelve populations that contributed significantly to mixed stock fisheries with the Ivalojoki river system being the major contributor (70%) to the total catch. When the contribution of wild trout populations to the fisheries was evaluated regionally, geographically nearby populations were the main contributors to the local catches. MSA also revealed a clear separation between the lower and upper reaches of Ivalojoki river system – in contrast to lower reaches of the Ivalojoki river that contributed considerably to the catch, populations from the upper reaches of the Ivalojoki river system (>140 km from the river mouth) did not contribute significantly to the fishery. This could be related to the available habitat size but also associated with a resident type life history and increased cost of migration. The studies in my thesis highlight the importance of dense sampling and wide population coverage at the scale being studied and also demonstrate the importance of critical evaluation of the underlying assumptions of the population genetic models and methods used. These results have important implications for conservation and sustainable fisheries management of Finnish populations of European grayling and brown trout in the Inari basin.

Aplicação de adsorção para remover amônia de efluentes suinícolas pré-tratados

The aim of this work is to evaluate the use of natural zeolites to remove the NH4+ that remains in effluents from swine facilities which were submitted to physico-chemical and biological treatments. Experiments were made in batch made adding 5% (w/w) of adsorbent (0.6-1.3 and 3.0-8.0 mm) to synthetic and real swine facilities effluents. The results show that ammonium removal is influenced by adsorbent particle size and the presence of other ions in the effluent. The adsorption equilibrium was described by Langmuir as well as Freundlich isotherms and the kinetic data fitted well a pseudo-second order model.

Um novo procedimento de síntese da zeólita A empregando argilas naturais

This work proposes the synthesis of zeolite A by IZA standard proceedures starting from a natural clay. The clay was used in its natural form and after calcination at 900ºC. The resulting materials were characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM) and porosity analysis by nitrogen adsorption. Results showed low surface area for Na-A zeolite in sodium form, but a higher one in CaA based on the nitrogen accessibility. The presence of cubic crystals for the A phase was observed in the SEM micrographies. The new procedure starting from natural clay favors the formation of sodalite while that using the calcinated clay gives A.

Estudo da síntese da zeólita MCM-71

A new kind of material, denominated MCM-71, was synthesized and characterized by several complementary techniques: X Ray Diffractometry, textural analysis by nitrogen adsorption, Scanning electronic microscopy and infrared spectroscopy. MCM-71 zeolite was successfully synthesized by hydrothermal synthesis in the presence of triethanolamine. Mordenite phase as impurity was not detected, otherwise quartz was observed. The MCM-71 sample obtained presented a BET surface area of 20 m²/g in the as synthesized form and of 85 m²/g in protonic form. By SEM was observed crystals with rectangular shape with average size of 2 x 0,2 x 0,05 µm and this crystals were agglomerated in spherical particles with average diameter between 14 and 24 µm.

Vanadium-modified molecular sieves: preparation, characterization and catalysis

Vanadium-containing molecular sieves are redox catalysts and are good candidates as substitutes for oxide-supported V2O5 in a number of reactions. These materials have the advantage of presenting better dispersion of vanadium species, as well as shape-selective properties and controllable acidities. They may be prepared by one-pot synthesis or by post-synthesis methods and a number of techniques such as diffuse reflectance UV-visible spectroscopy, 51V nuclear magnetic resonance and electron paramagnetic resonance, to name but a few, have been used to characterize these materials. In this review, methods of preparation of vanadium-modified molecular sieves, their characterization and applications in catalysis are discussed.

Aplicação de zeólitas sintéticas como coadjuvante em formulação detergente

The study consists is the application of zeolites NaX, NaY and A as builder in detergent formulations to eliminate the hardness of water. Therefore, the adsorption of ions Ca+2 and Mg+2 were evaluated, and the effect of the cleaning action of the surfactant sodium dodecil sulfate (SDS) through tests of detergency. The experiments were conducted in bath system (with shaking) and quantification of metals was performed by atomic absorption spectrometry. Zeolite A showed the best results for adsorption of Ca++ and Mg++ with retention rates of around 90 and 70% respectively and acted positively on the action of cleaning the surfactant SDS.

Remoção de azul de metileno de solução aquosa usando zeólitas sintetizadas com amostras de cinzas de carvão diferentes

Batch sorption experiments were carried out to remove methylene blue from its aqueous solutions using zeolites synthesized from fly ashes as an adsorbent. The adsorbents were characterized by XFR, XRD and SEM. Nearly 90 min of contact time are found to be sufficient for the adsorption of dye to reach equilibrium. Equilibrium data have been analyzed using Langmuir and Freundlich isotherms and the results were found to be well represented by the Freundlich isotherm equation. Adsorption data were fitted to both Lagergren first-order and pseudo-second-order kinetic models and the data were found to follow pseudo-second-order kinetics.

Estudo da adsorção de compostos sulfurados empregando zeólitas contendo zinco

This paper deals with an adosrption of sulphur compounds employing zeolites containing zinc. The zeolites employed were commercial NaY and Beta. The zinc was incorporated in three levels: 0.5; 1.0 and 5%. The sulphur compounds studied were benzothiophene and dibenzothiofene. The results showed that both zeolites can be employed for adsorption of benzothiophene and dibenzothiophene. The Zn incorporation (0.5%) promotes an increase in zeolites adsorption ability. The DBT adsorbs more than BT, probably because it strongly interacts with zeolite structure. The BT adsorbs more in NaY than in beta probably because the NaY zeolite has a high intern volume. This is not observed for DBT.

Estudo e caracterização da zeólita OFF Tipo T empregando diferentes fontes de silício

Offretite T zeolite was synthesized using different source of Si (Ludox AS-30, Ludox LS-30 and Aerosil 200 Degussa). The obtained materials were characterized by different complementary techniques: XRD, textural analysis by N2 adsorption, IV, SEM and chemistry analysis. This zeolite has an intermediary structure between offretite and erionite zeolites. In all experiments offretite T phase was obtained. Offretite phase presenting better crystalility are obtained in synthesis with stirring and employing aerosil as silicon source. This zeolite presents a potencial application as catalyst for hydroisodewaxing process.

Avaliação sensorial de cachaça

The hedonic level of commercial cachaças, was evaluated by consumers and by a tasters. The results of sensorial methods analyzed trough Principal Components Analysis, Hierarchical Cluster Analysis and the Pearson linear correlation indicated that the best classified cachaças were produced in copper stills and aged in oak casks. By contrast the worst classified exhibited as the main features be not aged and high alcohol percentage. The index of preference is positively correlated with the intensity of yellow color, wood flavor, sweetness and fruit aroma. There is a negative preference correlation with the acidity, the taste of alcohol and bitterness.

Remoção de Pb2+ e Cr3+ em solução por zeólitas naturais associadas a rochas eruptivas da formação serra geral, bacia sedimentar do Paraná

The capacity of natural zeolites and its host rock (dacite) to remove Pb2+ and Cr3+ from aqueous solutions has been investigated. Results showed that both samples prefer to remove Pb2+ instead of Cr3+. Almost 100% of Pb2+ was removed from solutions with concentration until 50 mg L-1 and 100 mg L-1 of this metal, respectively by dacite and zeolite. The equilibrium of metals adsorption process was reached during the first 30 min by both materials. Na+ can be used to recover Pb2+, but not to remove Cr3+ from the treated samples. The Sips model showed a good fit for experimental data of this study.