Abstract Honey is a food of nutritional, medicinal and commercial importance. The physicochemical characteristics, pollen spectrum and mineral composition of eighteen honey samples obtained from regions (Cachoeira, Coqueiros, Maragojipe and Santiago do Iguape) near the Paraguaçu River, Bahia, Brazil were evaluated. Botanical families Asteraceae, Leguminosae, Malvaceae, Myrtaceae and Palmae were most frequently found. Five samples had water contents above the maximum limit established by the Brazilian legislation (> 20%). The mineral composition was determined by ICP OES, after microwave digestion. Ca, K, Mg and Na were measured (mg Kg-1) in the range from: 18.85 to 79.61; 366.74 to 1214.98; 12.46 to 44.59 and 11.56 to 85.39, respectively. Cu, Fe, Mn and Zn had variable concentration ranges, between 0.05 and 6.13 mg Kg-1. Al, Ba, Cd, Co, Cr, Ni, Pb, Se and V showed values below the LOD. Principal component analysis (PCA) and hierarchical cluster analysis (HCA) demonstrated that there are no similarities of mineral composition among honey samples.

In this study, inductively coupled plasma optical emission spectrometry (ICP OES) was used for multi-element analysis in five multimineral preparations from a dissolution test, in accordance with the United States Pharmacopeia (USP 34 method): apparatus 1, 75 rpm and 900 mL of 0.1 mol L-1 HCl. Element releases in all samples (minimum-maximum in %) were: Ca (14.5-28.2), Cr (54.5-68.0), Cu (2.9-10.0), Fe (4.0-34.3), Mg (6.0-25.2), Mn (2.6-51.2), V (0.0-51.4) and Zn (1.5-107.3). The concentrations of Al, Ba, Cd, Co, Mo, Pb and Se were below the limit of detection of ICP OES. Accuracy was assessed by microwave digestion and recovery values of 94-102%. USP 34 method indicates that not less than 75% of the elements described on the product label must be dissolved in 1 h. Only the release of Zn met the recommendations. The results indicated the need for greater quality control in multivitamin preparations. The dissolution test was validated in order to contribute to Brazilian and other pharmacopoeias.

This work describes the development of Analytical Chemistry in Brazil from the Brazilian Chemical Society (SBQ) foundation to the present days. Important historical facts were highlighted and data on the human resources formation, financial investments and scientific production were used to evaluate and contextualize the progress achieved. The evolution of the scientific events of the area was also presented. The survey shows that Analytical Chemistry has advanced a lot in these 40 years, occupying a prominent position in the international scenario. This growth is mainly due to the formation of qualified human resources, the organization of scientific societies and inductive policies. It was also verified that the quantitative advance was greater than the qualitative one. Thus, one of the challenges for the next years is to work at the knowledge frontier and increases the quality and impact of scientific production in Analytical Chemistry. The evolution of the area into current trends such as Nanoscience, Microfluidic, Omics, Chemometric, Green Chemistry and Chemical Speciation is also presented and discussed.

In this study, the elemental composition of nine medicinal plants and phytomedicines was evaluated by using axial view inductively coupled plasma optical emission spectrometry (ICP OES) after three digestion procedures: dry ashing (DA) and two wet digestions with a mineral acid (HNO3/H2O2) mixture on a conventional hot plate (CD), besides microwave digestion (MW). Accuracy was assessed from spinach leaves (CRM 1570a) and recovery values were in the range of 82 to 113.8%. Precisions, such as relative standard deviation (RSD), below 10% were reached. The MW procedure was preferred for its accuracy (recovery values of 94 to 102%), reduced contamination, increase in the efficiency of the decomposition process, lower residual acidity and reduced time required for digestion. The concentrations of analytes in the samples (minimum-maximum in μg g-1) were: Ca (100.71-462.20), Co (0.54-0.85), Cu (0.32-7.82), Fe (2.74-18.03), Mg (18.40-521.28), Mn (0.17-55.14), Ni (0.56-1.25) and Zn (2.96-20.92). The levels of Al, Ba, Cd, Cr, Mo, Pb, Se and V in all investigated samples were found to be below the limit of detection of ICP OES. The multielement analysis by ICP OES showed that the method is simple, fast and reliable for the multielement determination in medicinal plants and phytomedicines.

RESUMO: Martianthus leucocephalus é encontrada no semiárido nordestino e possui potencial farmacológico atribuído à produção de compostos voláteis. Este trabalho objetivou avaliar o efeito de doses de Cd (15, 30, 45 and 60µmol L-1), Cu (30, 60, 90 and 120µmol L-1) e Zn (150, 300, 450 and 600µmol L-1) no crescimento dessa espécie e na produção de compostos voláteis. Estacas apicais foram transferidas para bandejas plásticas contendo 6,0L de solução nutritiva e, após o enraizamento, foram submetidas aos tratamentos de Cd, Cu e Zn, durante 15 dias. Todos os metais avaliados reduziram a suculência e o crescimento de todas as partes de M. leucocephalus . Este efeito foi acompanhado pelo incremento das concentrações de Cd, Cu e Zn em todos os tecidos das plantas. Também foi observado que o teor de compostos voláteis, produzido por M. leucocephalus, foi aumentado apenas pelo Zn (86%).

ABSTRACT: Martianthus leucocephalus is found in the semi-arid Northeast of Brazil and has high pharmacological potential due to the production of volatile compounds. This study aimed to evaluate the Cd (15, 30, 45 and 60µmol L-1), Cu (30, 60, 90 and 120µmol L-1) and Zn (150, 300, 450 and 600µmol L-1) levels on the growth of this species and its volatile compounds production. Apical cuttings were placed in plastic trays containing 6.0L nutrient solution, and after rooting, they were submitted to Cd, Cu and Zn treatments for 15 days. All the metals evaluated reduced the succulence and growth of all parts of M. leucocephalus . This effect was accompanied by the increase of Cd, Cu and Zn concentrations in all plant tissues. Volatile compounds content produced by M. leucocephalus was increased only by Zn (86%).

A simple, fast and inexpensive method was developed to determine essential elements in pellets of rice samples using energy dispersive X-ray fluorescence spectrometry (EDXRF). The accuracy and precision were evaluated using Standard Reference Material (rice flour NIST 1568a), and yielding relative standard deviation below 5%. The paired t-test showed good agreement within 95% confidence values. The detection limits (3σ) of Mn and Zn were 5.1 and 2.2 mg kg-1, respectively. The proposed method proved to be effective when used to determine Mn and Zn in commercial samples of rice without go by stage of decomposition.

Desenvolveu-se um procedimento para determinação de cobre, ferro, chumbo e zinco em amostras de gasolina. O procedimento foi baseado na pré-concentração dos metais empregando uma resina modificada com o ácido 3,4-dihidroxibenzóico (XAD-DHB), seguida da dessorção com solução ácida. Os analitos no eluato foram determinados por espectrometria de absorção atômica em chama multielementar seqüencial (FS-FAAS). As amostras de gasolina foram preparadas como microemulsões misturando-se 80 mL de amostra com 17 mL de propan-1-ol e 3 mL de solução tampão (pH 10). As variáveis físico-químicas que influenciam no processo de extração foram otimizadas. Os LODs obtidos foram 2,2 µg L-1 para Fe, 3,1 µg L-1 para Cu, 2,3 µg L-1 para Pb, e 2,6 µg L-1 para Zn. Os valores de RSDs das concentrações dos analitos nas amostras enriquecidas com 0,05 e 0,1 mg L-1 de cada metal variaram de 5,8 a 9,7%. As recuperações variaram de 82 a 99%. O método foi aplicado na determinação dos analitos em níveis de µg L-1 em amostras de gasolinas coletadas em postos revendedores de Salvador, BA, Brasil.

A procedure was developed for determination of copper, iron, lead and zinc in gasoline. The procedure was based on the preconcentration of metals using a resin modified with 3,4-dihydroxybenzoic acid (XAD-DHB), followed by desorption with an acid eluent. The components in the eluate were then determined by fast sequence flame atomic absorption spectrometry (FS-FAAS). The gasoline samples were prepared as microemulsions by mixing 80 mL of sample with 17 mL of propan-1-ol and 3 mL of a buffer solution (pH 10). The chemical and physical variables influencing the extraction were optimized. The LODs obtained were 2.2 µg L-1 Fe, 3.1 µg L-1 Cu, 2.3 µg L-1 Pb and 2.6 µg L-1 Zn. The RSDs ranged from 5.8 to 9.7% in samples spiked with 0.05 and 0.1 mg L-1 of each metal and recoveries varied from 82 to 99%. The procedure was suitable for determination of the analytes at µg L-1 levels in gasoline samples collected from several gas stations in Salvador, State of Bahia, Brazil.

Neste trabalho foi avaliada a eficiência de dois procedimentos para digestão ácida de amostras de biodiesel visando à determinação de Ca, P, Mg, K e Na por espectrometria de emissão óptica com plasma acoplado indutivamente com configuração axial (ICP OES). Nas digestões em sistema aberto, foi utilizada a mistura contendo ácidos nítrico, sulfúrico e peróxido de hidrogênio e aquecimento condutivo; enquanto que no procedimento empregando forno de microondas com cavidade foi utilizada a mistura contendo ácido nítrico e peróxido de hidrogênio. Os procedimentos foram avaliados considerando-se limites de quantificação, precisão, acidez final dos digeridos e teor de carbono residual. Os teores de carbono residual nos digeridos foram 0,358 ± 0,012% para o sistema aberto com aquecimento convencional e 0,614 ± 0,023% para o sistema fechado com aquecimento assistido por radiação microondas, o que demonstra a alta eficiência dos procedimentos propostos. O sistema de digestão em forno de microondas com cavidade resultou em maior rapidez, segurança e resultados analíticos com percentuais de recuperação de 89,0-103,0% e desvios menores que 5%. Os limites de detecção obtidos, < 0.40 µg g-1, são adequados para a determinação dos analitos, conforme os limites estabelecidos na legislação brasileira. Três amostras de biodiesel produzidas de diferentes fontes foram analisadas. Em comparação com outros procedimentos propostos na literatura, o procedimento desenvolvido usando forno de microondas com cavidade apresenta vantagens, tais como não necessitar de soluções orgânicas para calibração e não usar solventes orgânicos tóxicos.

In the present work, the efficiency of two procedures for the digestion of biodiesel was investigated for the simultaneous determination of Ca, P, Mg, K and Na by axial view ICP OES. In the open system with conventional heating, concentrated nitric and sulfuric acids were added to the samples, and the addition of hydrogen peroxide completed the digestion. In the microwave-assisted closed system, complete digestion was performed using concentrated nitric acid and hydrogen peroxide. The analytical performances were evaluated through limits of quantification, precision of the overall procedures, final acidity of the digests, and residual carbon contents. The contents of residual carbon for the biodiesel samples digested were 0.358 ± 0.012% using the open system with conventional heating and 0.614 ± 0.023% using the microwave-assisted closed vessel system, demonstrating the high efficiency of both proposed procedures. The optimized microwave-assisted decomposition procedure produced the fastest, safest and most accurate analytical results with recoveries of 89.0-103.0% and deviations lower than 5% in most cases. Low limits of detection were obtained (< 0.40 µg g-1), adequate for the established limits set out in Brazilian legislation for these analytes. Three biodiesel samples produced from different oil sources were analyzed. In comparison with other procedures proposed in the literature, the developed procedure using the microwave-assisted closed system is advantageous because it neither require organic standard solutions for calibrations nor use toxic organic solvents.

Neste trabalho descreve-se a composição mineral das folhas de Lippia alba (Mill.) que são utilizadas na preparação de chá utilizado na medicina popular. Assim, as folhas da espécie foram coletadas em cidades brasileiras e as amostras foram digeridas usando ácido nítrico e peróxido de hidrogênio em placa aquecedora e, em seguida, foram analisadas empregando espectrometria de emissão óptica com plasma acoplado indutivamente (ICP OES). Para avaliação da exatidão foi utilizado o material de referência certificado, folhas de maçã - NIST SRM 1515. Os resultados demonstraram que cálcio, magnésio e fósforo têm conteúdo médio de 1.950, 2.856 e 2.335 mg 100 g-1 e variações de concentrações de 767-3.887, 314-8.591 e 247-9.214 mg 100 g-1, respectivamente. Os micro-elementos, bário, zinco, cobre, ferro, manganês e níquel têm conteúdos médios de 2,16; 2,95; 0,94; 11,2; 4,25 e 0,09 mg 100 g-1, para variações de concentrações de 0,66-7,1; 1,35-6,3; 0,33-1,7; 0,98-34; 0.82-7,4 e 0,03-0,15 mg 100 g-1, respectivamente. Os dados foram também avaliados usando análise de componentes principais (PCA).

Leaves of Lippia alba (Mill.) N.E. Brown are used for the preparation of tea infusions that are employed in folk medicine. In this paper, the mineral composition of Lippia alba (Mill.) leaves, collected from different Brazilian cities, was evaluated. The samples were digested using nitric acid and hydrogen peroxide on a hot plate and were analyzed using inductively coupled plasma optical emission spectrometry (ICP OES). SRM 1515 apple leaves from NIST were used for checking accuracy. The results demonstrated that calcium, magnesium and phosphorus have average contents of 1,950, 2,856 and 2,335 mg 100 g-1, respectively, and concentration ranges of 767-3,887, 314-8,591 and 247-9,214 mg 100 g-1, respectively. The microelements barium, zinc, copper, iron, manganese and nickel have average contents of 2.16, 2.95, 0.94, 11.2, 4.25 and 0.09 mg 100 g-1, respectively, and concentration ranges of 0.66-7.1, 1.35-6.3, 0.33-1.7, 0.98-34, 0.82-7.4 and 0.03-0.15 mg 100 g−1, respectively. The data were also evaluated using principal component analysis (PCA).

Uma análise de variância de três fatores foi usada para testar a significância do tipo de recipiente, tipo de material e número de replicatas na preparação de amostras de sedimento utilizando um banho ultra-sônico. A extração convencional com HCl 1,0 mol L-1, por 0,5, 4 e 12 h, foi modificada, e o banho ultra-sônico foi aplicado para diminuir o tempo de preparo de amostras. Os metais traço foram medidos por ICP OES. Os melhores resultados foram obtidos com frascos de Teflon® com base plana. Com exceção do Ni, constatou-se que é possível trabalhar no banho de ultrasom em triplicatas, sem comprometer a eficiência e/ou precisão da extração. A eficiência de extração melhorou com o aumento no tempo de sonicação de 1 para 50 min. Para a maioria dos elementos, a extração assistida por radiação ultra-sônica pode reduzir o tempo convencional de extração de 12 h para 50 min ou menos (i.e. 6 min para Pb). A precisão obtida foi comparável aos valores obtidos com a extração convencional. O método proposto é rápido, barato e uma boa alternativa para o levantamento da biodisponibilidade e potencial de mobilidade de metais em sedimentos.

A three factors analysis of variance was used to test the significance of the type of vessel, the type of material and the number of replicates in the preparation of sediment samples using an ultrasonic bath. The conventional extraction with HCl 1.0 mol L-1, for 0.5, 4 and 12 h, has been modified, applying an ultrasonic bath, in order to speeding up the sample preparation time. Trace metals were measured by an ICP OES. The best results were obtained using a Teflon® vessel with a flat bottom. For all metals but Ni it was demonstrated the feasibility of working in triplicates in the ultrasonic bath, without compromising the efficiency and/or the precision of the extraction. Leaching efficiency enhanced with increasing sonication time from 1 to 50 min. For most elements the ultrasound-assisted leaching could reduce the conventional extraction time from 12 h to 50 min or even less (i.e. 6 min for Pb). The precision obtained was comparable to values obtained for the conventional acid extraction. The proposed method is a fast, inexpensive and easy alternative for screening of the potential mobility and bioavailability of metals in sediments.

Contextualized overview of the Biodiesel Production Chain, from the lab bench to the industry, with critical evaluation of state-of-art and technological development through scientific articles and patents, focusing on feedstock, reaction/production, first and second generation processes, specification and quality, transport, storage, co-products (effluents and sub-products), and emissions. Challenges are identified and solutions are proposed based on the Brazilian feedstock, edaphoclimatic conditions, process monitoring in remote regions, state policy, and environment preservation, among others. Forecasts are made based on the technology assessment, identifying future trends and opportunities for R&D&I.

Neste trabalho, foi avaliada a composição mineral da farinha de trigo consumida no Brasil. Na etapa de amostragem foram coletadas 54 amostras em 15 cidades, incluindo as principais cidades brasileiras como: São Paulo, Rio de Janeiro, Salvador, Porto Alegre, Recife e outras. Os elementos determinados foram: cálcio, cobre, magnésio, manganês, ferro, fósforo, potássio e zinco. As amostras foram digeridas usando acido nítrico e peróxido de hidrogênio em sistema aberto. A técnica analítica empregada foi a espectrometria de emissão óptica com plasma indutivamente acoplado (ICP OES). A validação do método (incluindo digestão e determinação) foi confirmada usando um material de referência certificado de farinha de trigo fornecido pelo National Institute of Standards & Technology (NIST). Considerando as 54 amostras analisadas, os resultados demonstraram que os macronutrientes: cálcio, magnésio, potássio e fósforo encontram-se em média de 0,27; 0,35; 1,71 e 1,92 mg g-1, com variação da concentração de 0,11-1,96; 0,19-0,51; 0,76-3,16 e 0,81-7,15 mg g-1, respectivamente. Os micronutrientes: cobre, ferro, manganês e zinco encontram-se em média de 1,84; 37,82; 8,25 e 9,41 µg g-1, com a variação de concentração de 1,00-2,80; 10,46-146,58; 3,89-14,74 e 5,07-13,93 µg g-1, respectivamente. Os resultados foram também avaliados usando as técnicas de análise multivariadas: análise de componente principal (PCA) e análise de agrupamento hierárquico (HCA).

In the present paper, the mineral composition of wheat flour consumed in Brazil was evaluated. In the sampling step 54 samples were collected in 15 cities, including principal Brazilian cities such as: São Paulo, Rio de Janeiro, Salvador, Porto Alegre, Recife and others. The elements determinate were: calcium, copper, magnesium, manganese, iron, phosphorus, potassium and zinc. The samples were digested using nitric acid and hydrogen peroxide in open system. The analytical technique employed was Inductively Coupled Plasma Optical Emission Spectrometry (ICP OES). The method validation (including digestion and determination) was performed using a certified reference material of wheat flour furnished by National Institute of Standards & Technology (NIST). Considering the 54 samples analyzed, the results demonstrated that the macronutrients: calcium, magnesium, potassium and phosphorus have average contents of 0.27, 0.35, 1.71 and 1.92 mg g-1, for concentration ranges of 0.11-1.96, 0.19-0.51, 0.76-3.16 and 0.81-7.15 mg g-1, respectively. The micronutrients: copper, iron, manganese and zinc have average contents of 1.84, 37.8, 8.2 and 9.4 µg g-1, for concentration ranges of 1.00-2.80, 10.5-146.6, 3.9-14.7 and 5.1-13.9 µg g-1, respectively. The results were also evaluated using the multivariate analysis techniques: principal component analysis (PCA) and hierarchical cluster analysis (HCA).

Neste trabalho a otimização de um procedimento rápido e de baixo custo para digestão ácida de feijão foi desenvolvida. Elementos essenciais (Ca, Cu, Fe, K, Mg, Mn, Ni, P, Zn) e não essenciais (Al, Ba, Sr) foram determinados por espectrometria de emissão óptica com plasma indutivamente acoplado (ICP OES). Foi utilizado planejamento fatorial de dois níveis fracionário com cinco fatores (volumes de HNO3 e H2O2, tempo, temperatura do bloco e tamanho de partícula). O fator temperatura foi o parâmetro mais importante e o planejamento Doehlert foi aplicado para determinar as condições ótimas, que foram obtidas quando se utiliza 3,5 mL de HNO3 concentrado e o tempo de 45 min. A exatidão foi demonstrada usando um material de referência certificado (folhas de espinafre NIST 1570a) e método oficial recomendado. Os resultados obtidos para todos os analitos foram concordantes com os valores certificados de acordo com o teste-t pareado para um nível de confiança de 95%.

In this work, the optimization of a fast and inexpensive acid wet digestion procedure for beans was developed. Essential (Ca, Cu, Fe, K, Mg, Mn, Ni, P, Zn) and non-essential (Al, Ba, Sr) elements were determined in beans degestates by inductively coupled plasma optical emission spectrometry (ICP OES). Experimental designs for five factors (HNO3 and H2O2 volume, digestion time, block temperature and particle size) were used for optimization of the digestion procedure, adopting a factorial experiment with 2(5-1) design. The factor block temperature was found to be the most important parameter and Doehlert designs were applied in order to determine the optimum conditions. Decomposition conditions were attained using 3.5 mL of concentrated HNO3 and lasts 45 min. The accuracy of the results was demonstrated using one certified reference material (spinach leaves NIST 1570a) and comparison with recommended official method. A paired t-test showed a good agreement for all analytes at 95% confidence values.

No presente trabalho foram avaliados os processos sortivos dos íons Cd2+ e Pb2+ em carne bovina em pH 6. Uma válvula de seleção de 8 canais foi utilizada para a mecanização do preparo das amostras e as concentrações de cádmio e chumbo foram determinadas por ICP-OES. Observou-se alta retenção (> 80%, m/m) dos íons Cd2+ e Pb2+ em carne fresca ou putrefata, indicando os riscos associados ao consumo de carne inadequadamente abatida, manipulada, estocada e/ou comercializada. Ácido acético a 1% (v/v) disponibilizou 70% do cádmio inicialmente adsorvido nas amostras de carne, revelando que práticas culinárias podem influenciar na sorção dos contaminantes.

The metal sorption capacity in fresh and rotten red meat was evaluated for Cd2+ and Pb2+ ions at pH 6 and the process involved in the studied metal retention was discussed. For the experimental set, an eight channels multi-port selection valve was employed to mechanise the sample preparation. The cadmium and lead concentrations were determined by ICP-OES. A high retention (> 80%, m/m) of Cd2+ and Pb2+ ions, in fresh and rotten bovine muscle was found, indicating the potential contamination risks related to the consumption of meat submitted to inappropriate conditions of abattoir, handling, storage and commercialisation. Seventy per cent of the cadmium was released with the immersion of meat in acetic acid at 1% (v/v), revealing that cookery practices may act on contaminant sorptive processes in meat structure.

Os materiais de controle de qualidade (QCM) têm sido usados rotineiramente no trabalho de laboratório, para preencher a lacuna entre a necessidade e disponibilidade de materiais de referência certificados (CRM). Os QCMs possuem custos relativamente baixos, quando comparados aos materiais de referência certificados (CRMs), sendo uma alternativa viável para a implementação de um sistema de controle de qualidade em laboratórios de várias áreas. Este trabalho descreve a produção de um QCM para determinação de metais em sedimentos estuarinos e os resultados de um exercício interlaboratorial. Estudos de homogeneidade e estabilidade foram realizados, e análises de variância foram aplicadas aos dados. As concentrações de Co, Cu, Cr, Ni, Mn, Pb e Zn, dentro e entre recipientes não foram significativamente diferentes. As condições de armazenagem e temperatura não promoveram variação nos resultados. O QCM produzido foi considerado estável e homogêneo, e pode ser utilizado em cartas de controle de qualidade, avaliação da reprodutibilidade e exercícios interlaboratoriais.

Quality Control Materials (QCM) have being used routinely in daily laboratory work as a tool to fill the gap between need and availability of Certified Reference Materials (CRM). The QCM are a low-cost alternative to CRMs, and they are in high demand, especially, for the implementation of quality control systems in laboratories of several areas. This paper describes the preparation of a QCM for the determination of trace metals in estuarine sediments and the results of an interlaboratory exercise. Homogeneity and stability studies were performed and analysis of variance was carried out with the results. No statistical significant differences were observed in the concentrations of Co, Cr, Cu, Mn, Pb and Zn between- or within bottle results. Neither the storage nor temperature affected the results. Therefore, the QCM produced is considered homogeneous and stable and can be used for statistical control charts, evaluation of reproducibility and interlaboratory exercises.