Rennan Geovanny Oliveira Araujo

Slurry Sampling—An Analytical Strategy for the Determination of Metals and Metalloids by Spectroanalytical Techniques

Abstract This article critically overviews the state-of-the-art of slurry sampling as an approach for the minimization of sample preparation prior to the determination of metals and metalloids in complex matrices by spectroanalytical techniques. Relevant factors involved in the optimization of slurry-based analytical procedures and the dependence of the quality of the results on the calibration method selected are discussed in detail. The advantages and limitations compared to solid sampling for the analysis of solid matrices are highlighted and discussed. Analytical applications of slurry sampling reported in the literature emphasizing publications between 2004 and 2009 are comprehensively compiled covering detection by flame atomic absorption spectrometry (FAAS), electrothermal atomic absorption spectrometry (ET-AAS), cold vapor atomic absorption spectrometry (CV-AAS), hydride generation atomic absorption spectrometry (HG-AAS), hydride generation atomic fluorescence spectrometry (HG-AFS), inductively coupled plasma optical emission spectrometry (ICP-OES), and inductively coupled plasma mass spectrometry (ICP-MS).

Simultaneous determination of Cd and Fe in beans and soil of different regions of Brazil using high-resolution continuum source graphite furnace atomic absorption spectrometry and direct solid sampling.

A fast routine screening method for the simultaneous determination of cadmium and iron in bean and soil samples is proposed, using high-resolution continuum source graphite furnace atomic absorption spectrometry and direct solid sampling. The primary absorption line at 228.802 nm has been used for the determination of cadmium, and an adjacent secondary line, at 228.726 nm, for iron. Fourteen bean samples and 10 soil samples from nine states all over Brazil have been analyzed. The limits of detection (3 sigma, n = 10) were 2.0 microg kg(-1) for Cd and 4.5 mg kg(-1) for Fe. The relative standard deviation ranged from 4 to 7% for Cd and from 5 to 28% for Fe, which is usually acceptable for a screening method. The accuracy of the method has been confirmed by the analysis of two certified reference materials; the results were in agreement with the certified values at a 95% confidence interval.

Multivariate optimization of an analytical method for the analysis of dog and cat foods by ICP OES.

Experimental design methodology was used to optimize an analytical method for determination of the mineral element composition (Al, Ca, Cd, Cr, Cu, Ba, Fe, K, Mg, Mn, P, S, Sr and Zn) of dog and cat foods. Two-level full factorial design was applied to define the optimal proportions of the reagents used for microwave-assisted sample digestion (2.0 mol L(-1) HNO3 and 6% m/v H2O2). A three-level factorial design for two variables was used to optimize the operational conditions of the inductively coupled plasma optical emission spectrometer, employed for analysis of the extracts. A radiofrequency power of 1.2 kW and a nebulizer argon flow of 1.0 L min(-1) were selected. The limits of quantification (LOQ) were between 0.03 μg g(-1) (Cr, 267.716 nm) and 87 μg g(-1) (Ca, 373.690 nm). The trueness of the optimized method was evaluated by analysis of five certified reference materials (CRMs): wheat flour (NIST 1567a), bovine liver (NIST 1577), peach leaves (NIST 1547), oyster tissue (NIST 1566b), and fish protein (DORM-3). The recovery values obtained for the CRMs were between 80 ± 4% (Cr) and 117 ± 5% (Cd), with relative standard deviations (RSDs) better than 5%, demonstrating that the proposed method offered good trueness and precision. Ten samples of pet food (five each of cat and dog food) were acquired at supermarkets in Aracaju city (Sergipe State, Brazil). Concentrations in the dog food ranged between 7.1 mg kg(-1) (Ba) and 2.7 g kg(-1) (Ca), while for cat food the values were between 3.7 mg kg(-1) (Ba) and 3.0 g kg(-1) (Ca). The concentrations of Ca, K, Mg, P, Cu, Fe, Mn, and Zn in the food were compared with the guidelines of the United States Association of American Feed Control Officials (AAFCO) and the Brazilian Ministry of Agriculture, Livestock, and Food Supply (Ministério da Agricultura, Pecuária e Abastecimento-MAPA).

Evaluation of trace metal levels in surface sediments of the Sergipe River Hydrographic Basin, Northeast Brazil

The distributions of Co, Cr, Cu, Mn, Ni, Pb, Fe and Al were investigated in surface sediments collected at 19 sites in the Sergipe River Hydrographic Basin of Northeast Brazil. A regional geochemical baseline (RGB) was defined using iron as a reference element. Enrichment factors (EF) and geoaccumulation indices (Igeo) were used to determine the extent of anthropogenic metal pollution. EF values showed that sediments from sites 1, 5 and 13 could be considered contaminated by Pb, Cr and Cu, respectively. Igeo values showed that only site 13 could be considered contaminated. For other sites, results indicated that naturally occurring metals predominated in the sediments. Possible toxicity related to these metals was examined using the comparing sediment chemical data with sediment quality guidelines (SQG) PEC-TEC values. Principal component analysis (PCA) clearly separated the sites into two groups and hierarchical cluster analysis (HCA) confirmed the interpretations made from the PCA results.

Determination of Zn in Dry Feeds for Cats and Dogs by Energy-Dispersive X-Ray Fluorescence Spectrometry

This work describes an analytical method for Zn determination in dry feeds for cats and dogs by energy-dispersive X-ray fluorescence (EDXRF). Samples of dry feed were powdered and prepared in the form of pellets for direct analysis by EDXRF. The LOQ (10σ) was 0.4 mg/kg. The samples were also analyzed by inductively coupled plasma-optical emission spectrometry (ICP-OES) as an independent comparative method. Application of a paired t-test showed no significant differences between Zn concentrations obtained by EDXRF and ICP-OES (at a 95% confidence level). Analysis of variance was also applied to the results and revealed no significant differences between the two techniques (at a 95% confidence level). The precision, expressed as the RSD (n = 3), was RSD < 4.55%. This analytical method provides a simple, rapid, accurate, and precise determination of Zn in dry feeds for cats and dogs by EDXRF as direct, solid-sample analysis.

Optimization method for sequential determination of Cu and Fe in airborne particulate matter collected on glass fiber filters by slurry sampling FAAS

Um metodo para determinacao sequencial de Cu e Fe em material particulado atmosferico (APM) coletado em filtro de fibra de vidro por amostragem em suspensao e espectrometria de absorcao atomica com chama e proposto. A otimizacao do metodo foi realizada utilizando-se uma massa de amostra seca em po (filtro + APM) de 50 mg, dispersa em solucao de acido nitrico 0,5 mol L-1 e tratada por 10 min em banho ultrassonico. Os limites de deteccao (n = 10) foram 4 e 14 µg g-1 para Cu e Fe no filtro, respectivamente. A repetitividade expressa como desvio padrao relativo foi melhor do que 7 e 8% (n = 3) para Cu e Fe, respectivamente. A exatidao do metodo foi confirmada analisando-se material de referencia certificado de cinzas atmosfericas (BCR 176R). Os resultados obtidos para seis amostras de APM utilizando o metodo proposto nao apresentaram diferencas significativas em comparacao com os valores obtidos usando o metodo de extracao acida e determinacao por espectrometria de massas com plasma indutivamente acoplado. O metodo analitico mostrou-se simples, rapido e confiavel.

Critical Evaluation of Analytical Procedures for the Determination of Lead in Seawater

Abstract: This article presents a critical evaluation of the analytical procedures used for the determination of lead in seawater, which is important because lead is a good indicator of marine pollution caused by human activities. Sampling, storage, and pretreatment techniques are briefly overviewed, including the significance of systematic errors that cannot be corrected later on. The main techniques in this article are electrothermal–atomic absorption spectrometry (ET-AAS), inductively coupled plasma–mass spectrometry (ICP-MS), and voltammetry. Flame atomic absorption spectrometry (FAAS) and inductively coupled plasma–optical emission spectrometry (ICP-OES) are treated as well, although their limits of quantification are not sufficient for a determination of lead in unpolluted seawater. Even when separation and preconcentration techniques are applied, these techniques are only capable of detecting lead in polluted coastal seawater. Separation and preconcentration are actually also required for ET-AAS and ICP-MS in order to determine the lowest concentrations of lead found in unpolluted open-ocean seawater, which is still a challenge for the analytical chemist.

Multivariate Optimization of Conditions for Digestion of Wet Feeds for Dogs and Cats Using a Closed Digester Block and Multielement Determination by ICP-OES

A full 24 factorial design was applied to find the best combination of diluted reagents (HNO3 and H2O2), time, and temperature for the digestion of samples of wet feed for dogs and cats using a closed digestion block. The residual carbon concentration (RCC) was used as the response in the factorial design. All variables and their interactions significantly influenced the digestion of the feed samples, as indicated by the RCC. The conditions established for the digestion of 0.05 g (dry mass) wet feed samples were the addition of 3.0 mol/L HNO3 and 5.0% m/m H2O2 in a final volume of 10 mL, followed by heating in a closed digestion block at a temperature of 170°C for 120 min. Analyses were performed by inductively coupled plasma (ICP) optical emission spectrometry (OES). LOQs ranged from 0.2 μg/g (Mg and Sr) to 51 μg/g (P). Accuracy of the analytical method was confirmed through the analysis of the Standard Reference Materials Tomato Leaves (NIST 1573), Apple Leaves (NIST 1515), and Peach Leaves (NIST 1547). The agreement values achieved ranged from 80.2 ± 0.3% for Ba to 113.8 ± 7.1% for Zn (n = 3). Addition and recovery tests were carried out by adding the analytes to a feed sample at two concentration levels, and the recoveries were between 84 ± 6 and 114 ± 10% for macroelements (Ca, K, Mg, and P; n = 3) and between 88 ± 3 and 113 ± 7% for microelements and trace elements (B, Cu, Fe, Sr, and Zn; n = 3). The precision values achieved for the different elements, expressed as RSDs, were better than 7.3% (Zn; n = 3) except for Cu determination, that was 14.6% (n=3). The optimized analytical method was applied to 10 commercial samples of wet feed for cats and dogs, with the concentrations of Al, B, Ba, Ca, Cu, Fe, K, Mg, Mn, P, Sr, and Zn determined by ICP-OES.

GEOCHEMICAL CORRELATIONS BETWEEN PETROLEUM SAMPLES FROM THE POTIGUAR BASIN AND DEFINITION OF THEIR POSSIBLE GENERATING ROCKS

Jeferson Cavalcante Alvesa, Rennan Geovanny Oliveira Araujoa,b,*,#, Eliane Soares de Souzac, Sarah Adriana Rocha Soaresa, José Roberto Cerqueiraa, Karina Santos Garciaa, Antonio Fernando de Souza Queiroza, Maria Goreti Rodrigues Valed e Aline Rocha Borgese Núcleo de Estudos Ambientais, Instituto de Geociências, Universidade Federal da Bahia, Campus de Ondina, Rua Barão de Jeremoabo, s/n – Ondina, 40170-110 Salvador – BA, Brasil Departamento de Química Analítica, Instituto de Química, Universidade Federal da Bahia, Campus Ondina, Rua Barão de Jeremoabo, 147 – Ondina, 40170-115 Salvador – BA, Brasil Laboratório de Engenharia e Exploração de Petróleo, Centro de Ciências e Tecnologia, Universidade Estadual do Norte Fluminense, Rodovia Amaral Peixoto Km 163, Avenida Brennand s/n – Imboacica, 27925-310 Macaé – RJ, Brasil Instituto de Química, Universidade Federal do Rio Grande do Sul, Av. Bento Gonçalves 9500, 91501-790 Porto Alegre – RS, Brasil Instituto Federal do Paraná, Campus Palmas, 85555-000, Palmas – PR, Brasil

Evaluation of the Chemical Composition of Dry Feeds for Dogs and Cats

Cat and dog feed production has increased worldwide, and much emphasis has been placed on the importance of determining the mineral composition of pet foods. In this work, the concentrations of Al, Ba, Ca, Cd, Cr, Cu, Fe, K, Mg, Mn, Ni, P, Sr, V and Zn in dry feed for cats and dogs employing inductively coupled plasma-optical emission spectrometry (ICP OES) were determined and evaluated according to regulatory agencies. Forty-one dry feed samples (24 dog feed and 17 cat feed) were analyzed. The obtained concentrations ranged from 2.3 mg kg (Ba) to 2.8 g kg (Ca) in cat feeds, and from 3.8 mg kg (Cu) to 3.4 g kg (Ca) in dog feeds. The concentrations of P are in accordance with the Brazilian legislation, and Mn and Zn contents met the American legislation. The concentration values of Cu, K and Mg presented in some samples were below the limits established by American regulatory agency. Based on multivariate data analysis evaluated from flavors of the products and brands, it was concluded that the feed samples were uniform since there was no trend to group formation and classification according to their mineral composition, except one dog feed brand, which had a significant content of Al and Cu.