Avaliação do uso de métodos quimiométricos em análise de solos

One of the major interests in soil analysis is the evaluation of its chemical, physical and biological parameters, which are indicators of soil quality (the most important is the organic matter). Besides there is a great interest in the study of humic substances and on the assessment of pollutants, such as pesticides and heavy metals, in soils. Chemometrics is a powerful tool to deal with these problems and can help soil researchers to extract much more information from their data. In spite of this, the presence of these kinds of strategies in the literature has obtained projection only recently. The utilization of chemometric methods in soil analysis is evaluated in this article. The applications will be divided in four parts (with emphasis in the first two): (i) descriptive and exploratory methods based on Principal Component Analysis (PCA); (ii) multivariate calibration methods (MLR, PCR and PLS); (iii) methods such as Evolving Factor Analysis and SIMPLISMA; and (iv) artificial intelligence methods, such as Artificial Neural Networks.

Aplicação de análise de componentes principais para verificação de atribuições de sinais nos espetros de RMN ¹H: o caso dos 3-aril (1,2,4)-oxadiazol-5-carboidrazida benzilidenos

The ¹H NMR data set of a series of 3-aryl (1,2,4)-oxadiazol-5-carbohydrazide benzylidene derivatives synthesized in our group was analyzed using the chemometric technique of principal component analysis (PCA). Using the original ¹H NMR data PCA allowed identifying some misassignments of the proton aromatic chemical shifts. As a consequence of this multivariate analysis, nuclear Overhauser difference experiments were performed to investigate the ambiguity of other assignments of the ortho and meta aromatic hydrogens for the compound with the bromine substituent. The effect of the 1,2,4-oxadiazol group as an electron acceptor, mainly for the hydrogens 12,13, has been highlighted.

Estudo multivariado de solos urbanos da cidade de Teresina

The concentrations of Cu, Pb, Zn, Cr, Ni, Al, Mn and Fe were measured by atomic absorption spectrometry, of 19 topsoil samples collected in the Teresina city urban area to discriminate natural and anthropic contributions and identify possible sources of pollution. The average concentrations of Cu, Zn, Pb and Cr of the urban soils were 6.11, 8.56, 32.12 and 7,17 mg/kg-1, respectively. Statistical analysis techniques, such as principal component analysis (PCA) and hierarchical cluster analysis (HCA), were used to analyze the data. Mn, Ni and Cr levels were interpreted as natural contributions, whereas Pb, Zn and, in part, Cu were accounted for mainly by anthropic activities. High Pb levels were observed in the ancient avenues.

Torrential rainfall in northeast of the Iberian Peninsula: synoptic patterns and WeMO influence

This study presents a catalogue of synoptic patterns of torrential rainfall in northeast of the Iberian Peninsula (IP). These circulation patterns were obtained by applying a T-mode Principal Component Analysis (PCA) to a daily data grid (NCEP/NCAR reanalysis) at sea level pressure (SLP). The analysis made use of 304 days which recorded >100 mm in one or more stations in provinces of Barcelona, Girona and Tarragona (coastland area of Catalonia) throughout the 1950-2005 period. The catalogue comprises 7 circulation patterns showing a great variety of atmospheric conditions and seasonal or monthly distribution. Likewise, we computed the mean index value of the Western Mediterranean Oscillation index (WeMOi) for the synoptic patterns obtained by averaging all days grouped in each pattern. The results showed a clear association between the negative values of this teleconnection index and torrential rainfall in northeast of the IP. We therefore put forward the WeMO as an essential tool for forecasting heavy rainfall in northeast of Spain

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.

Hidrocarbonetos policíclicos aromáticos como traçadores da queima de cana-de-açúcar: uma abordagem estatística

In this study atmospheric particulates of PAHs were measured in Araraquara, Piracicaba and São Paulo in July 2003 (sugarcane harvest season in Araraquara and Piracicaba) and in Araraquara in March of 2003. The results were normalized to the total PAH concentrations. Comparison among the sites and principal component analysis (PCA) were used to investigate possible tracers of emission. Fluoranthene and pyrene concentrations were higher in Piracicaba and Araraquara samples. These PAH were also responsible for the largest negative loadings on the second principal component and account for the negative scores and for the formation of the Araraquara and Piracicaba group.

Análise arqueométrica de cerâmica Tupiguarani da região central do Estado do Rio Grande do Sul, Brasil, usando fluorescência de raios X por dispersão de energia (EDXRF)

Energy dispersive X-ray fluorescence methodology (EDXRF) was used to determine Al, Ba, Ca, Cr, Fe, K, Mn, Pb, Rb, S, Si, Sr, Ti, V, Zn in pottery sherds from seven archaeological sites in the central region of Rio Grande do Sul State, Brazil. The potteries' chemical fingerprints from Ijuí River, Ibicuí Mirim River, Vacacaí Mirim River and Jacuí River were identified. Interactions between sites from the Jacuí River, Vacacaí Mirim River and Ibicui Mirim River could have occurred because some samples from these sites are overlapping in a principal component analysis (PCA) graphic. The pottery provenance could be the same.

Análisis psicométrico de la escala multidimensional de autoconcepto AF5 en una muestra de adolescentes y adultos de Cataluña

Psychometric analysis of the AF5 multidimensional scale of self-concept in a sample of adolescents and adults in Catalonia. The aim of this study is to carry out a psychometric study of the AF5 scale in a sample of 4.825 Catalan subjects from 11 to 63 years-old. They are students from secondary compulsory education (ESO), from high school, middle-level vocational training (CFGM) and from the university. Using a principal component analysis (PCA) the theoretical validity of the components is established and the reliability of the instrument is also analyzed. Differential analyses are performed by gender and normative group using a 2 6 factorial design. The normative group variable includes the different levels classifi ed into 6 sub-groups: university, post-compulsory secondary education (high school and CFGM), 4th of ESO, 3rd of ESO, 2nd of ESO and 1st of ESO. The results indicate that the reliability of the Catalan version of the scale is similar to the original scale. The factorial structure also fi ts with the original model established beforehand. Signifi cant differences by normative group in the four components of self-concept explored (social, family, academic/occupational and physical) are observed. By gender, signifi cant differences appear in the component of physical self-concept, academic and social but not in the family component

Análise por componentes principais de espectros nexafs na especiação do molibdênio em catalisadores de hidrotratamento

Bulk and supported molybdenum based catalysts, modified by nickel, phosphorous or tungsten were studied by NEXAFS spectroscopy at the Mo L III and L II edges. The techniques of principal component analysis (PCA) together with a linear combination analysis (LCA) allowed the detection and quantification of molybdenum atoms in two different coordination states in the oxide form of the catalysts, namely tetrahedral and octahedral coordination.

Aplicação de métodos quimiométricos na caracterização de charutos utilizando extração por dispersão da matriz em fase sólida e análise por cromatografia gasosa acoplada à espectrometria de massas

In this work, the organic compounds of cigar samples from different brands were analyzed. The compound extraction was made using the matrix solid-phase dispersion (MSPD) technique, followed by gas chromatography and identification by mass spectrometry (GC-MS) and standards, when available. Thirty eight organic compounds were found in seven different brands. Finally, with the objective of characterizing and discriminating the cigar samples, multivariate statistical analyses were applied to data, e.g.; principal component analysis (PCA) and hierarchical cluster analysis (HCA). With such analyses, it was possible to discriminate three main groups of three quality levels.

Caracterização estrutural das substâncias húmicas aquáticas extraídas dos rios itapanhaú e ribeira de iguape

The knowledge of the structure characteristic of the Organic Matter is important for the understanding of the natural process. In this context aquatic humic substances (principal fraction) were isolated from water sample collected from the two distinct rivers, using procedure recommended for International Humic Substances Society and characterized by elemental analysis, electron paramagnetic resonance and nuclear magnetic resonance (13C NMR). The results were interpreted using principal component analysis (PCA) and the statistical analyses showed different in the structural characteristics of the aquatic humic substances studied.

Experimento didático de quimiometria para análise exploratória de óleos vegetais comestíveis por espectroscopia no infravermelho médio e análise de componentes principais: um tutorial, parte I

This manuscript aims to show the basic concepts and practical application of Principal Component Analysis (PCA) as a tutorial, using Matlab or Octave computing environment for beginners, undergraduate and graduate students. As a practical example it is shown the exploratory analysis of edible vegetable oils by mid infrared spectroscopy.

Comparação do perfil químico entre cachaças de um mesmo vinho destiladas em alambiques e em colunas

Six wines were distilled in two different distillation apparatus (alembic and column) producing 24 distillates (6 for each alembic fraction - head, heart and tail; 6 column distillates). The chemical composition of distillates from the same wine was determined using chromatographic techniques. Analytical data were subjected to Principal Component Analysis (PCA) and Hierarchical Cluster Analysis (HCA) allowing discrimination of four clusters according to chemical profiles. Both distillation processes influenced the sugarcane spirits chemical quality since two types of distillates with different quantitative chemical profiles were produced after the elimination of fermentation step influence.

Oxidação de glicerol sobre nanopartículas de ouro suportadas em carvão ativado: monitoramento quimiométrico da reação por ESI-MS e MIR

A study on the monitoring of glycerol oxidation catalyzed by gold nanoparticles supported on activated carbon under mild conditions by chemometric methods is presented. The reaction was monitored by mass spectrometry-electrospray ionization (ESI-MS) and comparatively by mid infrared spectroscopy (MIR). Concentration profiles of reagent and products were determined by chemometric tools such as Principal Component Analysis (PCA), Evolving Factor Analysis (EFA) and Multivariate Curve Resolution (MCR). The gold nanoparticle catalyst was relatively active in glycerol oxidation, favoring formation of high added value products. It was found that the reaction stabilization was reached at four hours, with approximately 70% glycerol conversion and high selectivity for glycerate.

Estudo da qualidade da gasolina tipo A e sua composição química empregando análise de componentes principais

The type A gasoline samples were analyzed by gas chromatography with flame ionization detector (GC-FID) which allowed quantifying and classifying of the various compounds into different classes of hydrocarbons. Several physicochemical parameters were evaluated according to the official methods in order to compare the results obtained against the limits established by the Agência Nacional de Petróleo, Gás Natural e Biocombustíveis (ANP, 2011). Additionally, principal component analysis (PCA) was applied to discriminate the samples studied, which revealed the separation of four groups according to their chemical composition determined in samples collected from the eight fuel distributors in the State of Pará.