This paper describes the evaluation of the total concentration of Ba, Bi, Ca, Cd, Co, Cr, Cu, Fe, K, Mn, Pb e Zn and the bioaccessible fraction of Ba, Cu, Fe, Mn, Pb and Zn in samples of grape skins from different cultivars (Vitis Viníferas Tannat and Cabernet Sauvignon) by MIP OES. For the determination of total concentration, acid decomposition with a reflux system adapted to the digestion tubes in the oxidizing medium of HNO3 and H2O2 were used. The accuracy of the method was verified by recovery tests, whose values ranged from 80 to 120%, as well as through a comparative method in closed system. Bi, Cd and Cr showed values for total content below the LOD or below the values acceptable for health while Pb is higher than 0.2 mg kg-1, for both cultivars. To evaluate the bioacessible fraction, the gastrointestinal system was simulated using an in vitro procedure, and its performance was assessed considering the bioaccessible fraction (supernatant) and the non-bioaccessible fraction, whose sum should be closed to the total concentration, and the results obtained were between 81 and 120%. Both cultivars showed similar values for the bioaccessible fractions (~13.5 – 53% of the total content).

RESUMO Objetivo: Determinar e comparar as concentrações de eletrólitos e minerais no leite humano em três grupos: amostras analisadas antes e após pasteurização de lactantes doadoras a termo e amostra de leite cru colhida à beira do leito de mães de recém-nascidos pré-termo. Métodos: Estudo descritivo de corte transversal. Foram dosadas concentrações de cálcio (Ca), fósforo (P), magnésio (Mg), sódio (Na) e potássio (K) em amostras aleatórias de leite humano nos três grupos. As amostras foram analisadas por mineralização ácida assistida por radiação micro-ondas e posteriormente por espectrometria de emissão óptica com plasma indutivamente acoplado e expressas em mg/L, com cálculo de médias e desvio padrão. A comparação entre os grupos foi feita por análise de variância (ANOVA)/teste de Tukey. Nível de significância aceito de 5%. Resultados: Observou-se redução significante dos teores de Ca (259,4±96,8 vs. 217,0±54,9; p=0,003), P (139,1±51,7 vs. 116,8±33,3; p=0,004) e K (580,8±177,1 vs. 470,9±109,4; p<0,0001) após a pasteurização. As amostras de leite cru colhidas à beira do leito apresentaram teores estatisticamente mais elevados de Na (2 vezes) do que o leite a termo de doadora. Ca e P só atingiriam a ingestão recomendada pela European Society of Pediatric Gastroenterology, Hepatology and Nutrition se o leite materno fosse ofertado em volume de 60 mL a cada 3 horas. Concentrações de Mg não diferiram entre os grupos. Conclusões: Houve uma redução significativa de Ca, P e K nas amostras após pasteurização e os valores de Na no leite cru coletado à beira do leito foram superiores àqueles pré-pasteurização.

ABSTRACT Objective: To determine and compare the concentrations of electrolytes and minerals in three different types of maternal milk samples: term donor milk before pasteurization, term donor milk after pasteurization and raw milk of mothers of preterm newborns at bedside. Methods: Descriptive cross-sectional study. Concentrations of calcium (Ca), phosphorous (P), magnesium (Mg), sodium (Na) and potassium (K) were measured in random samples of three human breast milk groups. Samples were analyzed using acid mineralization assisted by microwave radiation and further analysis by inductively coupled plasma optical emission spectrometry. Concentrations were expressed in mg/L, described as mean and standard deviation. The one-way ANOVA and Tukey’s post-test were applied to determine the variability between the means of each group. Significance level was set at 5%. Results: There was a significant reduction in the content of Ca (259.4±96.8 vs. 217.0±54.9; p=0.003), P (139.1±51.7 vs. 116.8±33.3; p=0.004) and K (580.8±177.1 vs. 470.9±109.4; p<0.0001) in donor maternal milk before and after pasteurization. Samples of raw milk presented higher contents of Na than the donated milk (twice). The elements P and Ca would only reach the daily intake levels recommended by the European Society of Pediatric Gastroenterology, Hepatology and Nutrition if at least 60 mL of milk could be offered every 3 hours. Mg levels were not different between the three groups. Conclusions: There was a significant reduction in Ca, P and K levels in samples after pasteurization. The Na value in raw milk, collected at bedside, was higher than in the samples of donor’s milk before pasteurization.

The effect of selenate and selenite enrichment on mineral composition of a red type of lettuce cv. “Veneza roxa” was evaluated using inductively coupled plasma-optical emission spectroscopy (ICP OES), molecular modeling and principal component analysis (PCA). Both Se species did not show toxicity, while selenate promoted the greatest Se accumulation by the plant. There was an increase of 886 µg of Se per 100 g of fresh sample at different concentrations of selenate, but for selenite the maximum variation was only of 114 µg per 100 g. Selenate promoted the absorption of Mo and S and the reduction of K, Mn and P, meanwhile selenite increased Mn and decreased Mo accumulation. Copper and Fe absorption was negatively affected, Ca and Mg showed a slight increase, and Na and Zn were not affected by Se species. Despite the changes in the nutritional balance, Se-enriched lettuce can still be considered a potential dietary source of this essential element.

In the first part of this paper, two acid decomposition procedures for the determination of Al, Ca, Fe, Mg, Mn and Zn contents in yerba mate samples by inductively coupled plasma optical emission spectrometry (ICP OES) were compared. Using a reflux system, the samples were treated with a mixture of HNO3 and H2O2 for 3 hours at 220 °C in the digester block. The results from five commercial yerba mate samples were compared with the results obtained from microwave digestion. Good agreement between the procedures at a 95% confidence level was obtained with relative standard deviation (RSD) values lower than 10.0%. The accuracy was evaluated using addition and recovery experiments (80.5 to 112.8%). In the second part, Ca, Cd, Cr, Cu, Fe, K, Mg, Na, Pb and Zn concentrations were evaluated in the yerba mate infusion. The results showed that elements such as Na, K, Mg and Zn are easily transferred to the hot water used for the infusion. For Pb and Cd, the concentrations found in the analyzed samples were lower than the values established by Brazilian legislation.

In general, inductively coupled plasma mass spectrometry (ICP-MS) food analysis requires numerous sample treatment steps that imply an increase of analysis time and the use of chemicals. In this study, the main objective was to evaluate the applicability of the direct analysis by ICP-MS to determine twelve elements (Al, As, Ba, Cd, Cr, Cu, Fe, Mn, Ni, Pb, Se and Zn) in tea and herbal beverages. Direct analysis method was compared with two other sample treatments: minimum treatment (acid dilution) and using a destructive method (microwave assisted digestion). Besides the lowest time of analysis, direct analysis provides a reliable response and agrees with the “green chemistry” principles. High sensitivity was also observed by low values of limits of detection and quantification, in general, below 2.5 µg L-1. The method accuracy was evaluated by spiked experiments and values ranged between 82 and 120%. Low values of coefficient of variation were also observed, 2 to 17%, for all analytes. The method exhibited applicability for commercial tea samples as well as for drinks made by herb infusion.

A determinação de selênio, crômio e cobre em corantes alimentares por espectrometria de absorção atômica com forno de grafite foi feita utilizando-se uma simples dissolução ácida como tratamento de amostra. Modificadores químicos foram investigados para os três analitos. Utilizando calibração por compatibilização de matriz, temperaturas de pirólise e de atomização de 1300 e 1800 ºC, respectivamente, e 5 µg Pd + 3 µg Mg(NO3)2 como modificador químico foi possível a determinação de selênio em todos os corantes estudados. Para o crômio, 15 µg Mg(NO3)2 foram utilizados como modificador químico e as temperaturas de pirólise e atomização foram de 1500 e 2500 ºC, respectivamente, usando calibração externa. A determinação de cobre foi feita sob temperaturas ideais de pirólise (1200 ºC) e de atomização (2000 ºC) usando 5 µg Pd + 3 µg Mg(NO3)2 como modificador químico e, dependendo do corante, foi necessário o uso de calibração externa ou de adição de padrão. Valores de recuperação entre 90 e 110% foram obtidos com os métodos desenvolvidos. As análises dos corantes utilizados por indústrias alimentícias mostraram concentrações de Cu abaixo dos valores máximos recomendados pela legislação brasileira, no entanto, não existem limites estabelecidos para Se e Cr.

The determination of selenium, chromium and copper in food dyes by graphite furnace atomic absorption spectrometry was carried out using a simple acid dissolution as sample treatment. Different chemical modifiers were investigated for the three analytes. Using the matrix-matching calibration technique, pyrolysis and atomization temperatures of 1300 and 1800 ºC, respectively, and 5 µg Pd + 3 µg Mg(NO3)2 as chemical modifier allowed the determination of Se in all the studied dyes. For chromium, 15 µg Mg(NO3)2 were used as chemical modifier, and pyrolysis and atomization temperatures were of 1500 and 2500 ºC, respectively, using external calibration. The determination of copper was carried out under the optimized temperatures of pyrolysis (1200 ºC) and atomization (2000 ºC) using 5 µg Pd + 3 µg Mg(NO3)2 as chemical modifier and, depending on the dyes, it was necessary to use external or standard addition calibration. Recoveries between 90 and 110% were obtained for the developed methods. The analysis of dyes used by food industries showed concentrations of Cu below the maximum values recommended by Brazilian legislation, however, there are no established limits for Se and Cr.

As frações bioacessíveis de Al, Ba, Cd, Cr, Cu, Mg, Mn e P em amostras de achocolatado foram estimadas usando um método de digestão in vitro e técnicas espectrométricas de análise. Como método de digestão in vitro foi utilizado um procedimento de três etapas, nas quais são simulados os processos digestivos que ocorrem na boca, no estômago e no intestino com a preparação de fluidos digestivos sintéticos. Para o tratamento da amostra e do quimo (porção solúvel) obtido no método de digestão in vitro, utilizou-se mineralização assistida por radiação micro-ondas, considerando os altos teores de matéria orgânica. Os teores de Al, Ba, Cu, Mg, Mn e P foram quantificados por espectrometria de emissão óptica com plasma indutivamente acoplado, enquanto os teores de Cd e Cr foram quantificados por espectrometria de absorção atômica com forno de grafite. Considerando os teores totais dos elementos estudados, as frações bioacessíveis obtidas foram: 5 ± 3% para Al, 9 ± 2% para Ba, 13 ± 3% para Cd, 5 ± 2% para Cr, 29 ± 4% para Cu, 54 ± 3% para Mg, 11 ± 3% para Mn e 31 ± 6% para P. De uma maneira geral, elementos que desempenham funções essenciais no organismo humano apresentaram maior bioacessibilidade quando comparados aos elementos potencialmente tóxicos em níveis traços.

The bioaccessible fractions of Al, Ba, Cd, Cr, Cu, Mg, Mn and P in chocolate drink powder were estimated using an in vitro digestion method and spectrometric techniques. A three-step procedure was used as an in vitro digestion method, in which the digestive process occurring in the mouth, stomach and intestine are simulated with the preparation of synthetic digestive fluids. Mineralization assisted by microwave radiation was used for the treatment of the sample and the chyme (soluble portion) obtained in the in vitro digestion method, considering their high organic content. Aluminum, Ba, Cu, Mg, Mn and P were quantified by inductively coupled plasma optical emission spectrometry, whereas Cd and Cr were quantified by graphite furnace atomic absorption spectrometry. Considering the total content of these elements in chocolate drink powder, the bioaccessible fractions found were 5 ± 3% for Al, 9 ± 2% for Ba, 13 ± 3% for Cd, 5 ± 2% for Cr, 29 ± 4% for Cu, 54 ± 3% for Mg, 11 ± 3% for Mn and 31 ± 6% for P. In general, elements that perform essential functions in the human organism presented higher bioaccessibility when compared with potentially toxic elements at trace levels.

Foi desenvolvido um método de extração de íons de metais presentes em amostras de arroz, usando solução amoniacal de EDTA (ácido etilenodiamino tetraacético), pH > 10, como agente extrator, sob as seguintes condições otimizadas: 0,20 g de amostra de arroz e 5,00 mL da solução amoniacal de EDTA, com 5 min de tempo de exposição em ultrassom. Usando condições robustas de ICP OES (espectrometria de emissão atômica por plasma acoplado indutivamente), foi possível analisar a solução extraída, obtendo-se valores de recuperação acima de 90% para a maioria dos elementos estudados (P, K, Mg, Ca, Zn, Mn, Cu e Mo) com RSD < 5%. Os resultados mostraram concordância com aqueles obtidos por extração assistida por microondas e para o material de referência certificado de farinha de arroz (NIST SRM 1568a). Os limites de detecção do método ficaram no intervalo de 0,007 mg kg-1 (Mn) - 48,68 mg kg-1 (K), mostrando uma detectabilidade adequada para a determinação das espécies de interesse. A análise das diversas amostras indicou que o arroz brasileiro integral contém teores mais elevados dos constituintes estudados, seguido pelo arroz parboilizado e o arroz agulhinha.

A method for extraction of metal ions present in rice samples using ammoniacal EDTA solution, pH > 10, as extractor agent is proposed under the following optimized conditions: 0.20 g of rice sample and 5.00 mL of ammoniacal EDTA (ethylenediaminetetraacetic acid) solution, with 5 min of ultrasound exposure time. Using robust ICP OES (inductively coupled plasma atomic emission spectrometry) conditions, direct analysis of the extraction solution was allowed, and the recovery values obtained were above 90% for most of the studied elements (P, K, Mg, Ca, Zn, Mn, Cu and Mo) with RSD < 5%. The results were in good agreement with those obtained by microwave-assisted extraction and for the reference material of rice flour (NIST SRM 1568a). The limits of detection of method were in the range of 0.007 mg kg-1 (Mn) - 48.68 mg kg-1 (K), showing adequate detectability for the determination of the analytes. The analysis of different samples indicated that Brazilian "integral" rice contains higher contents of the constituents studied, followed by "parboiled" rice, and the "agulhinha" rice a long and thin grain type.

Neste trabalho estão descritos alguns métodos para a digestão de amostras de emulsão aquosa de acetato de polivinila visando à determinação de As, B, Cd, Cr, Cu, Fe, Hg, Ni, Pb e Sb por espectrometria de emissão óptica em plasma com acoplamento indutivo (ICP OES). Foram estudados métodos clássicos como calcinação, digestão ácida (a baixa temperatura e a alta temperatura) em chapa de aquecimento e também a digestão assistida por microondas (MW). Nas condições otimizadas (MW) obteve-se apenas 0,1% de conteúdo de carbono residual (RCC), recuperações das espécies estudadas entre 100 e 107 %, com RSD entre 0,5 e 2,5 % e limites de quantificação entre 0,003 e 0,29 mg kg-1.

Digestion method for the determination of As, B, Cd, Cr, Cu, Fe, Hg, Ni, Pb and Sb by inductively coupled plasma optical emission spectrometry (ICP OES) in samples of polyvinyl acetate water emulsions were developed. A comparison between classical methods like calcination, acid digestion (low temperature and high temperature) on a heating plate and microwave digestion (MW) was made. Under optimum conditions, using the MW procedure, only 0.1% of residual carbon content (RCC) was found as residue and recoveries between 100 and 107%, with RSD between 0.5 and 2.5% and quantification limits between 0.003 and 0.29 mg kg-1 were obtained.

Polymeric materials are widely used in the chemical industry and are part of our daily lives. Inorganic species may be added to them as additives, anti-oxidizing agents, stabilizers, plasticizers, colorants and catalysts and may be present in a wide range of concentrations. Their determination demands the development of analytical methods considering different kinds of polymeric materials, their composition and the final use of the material. Although many different analytical techniques may be used, this review emphasizes those based on atomic absorption and emission spectrometry. Solid sampling techniques and digestion methods are described and discussed and compared considering published results.

A determinação de espécies inorgânicas em adoçantes líquidos à base de ciclamato-sacarina e esteviosídeo é descrita. O método, sem tratamento prévio da amostra, é baseado na espectrometria de emissão óptica em plasma com acoplamento indutivo. Parâmetros instrumentais foram otimizados de acordo com a robustez do plasma e a razão sinal analítico/ sinal de fundo. A exatidão foi avaliada para As, Ca, Cd, Co, Cu, Fe, Mg, Mn, Ni, Pb e Zn empregando experimentos de adição e recuperação. Os valores de recuperação ficaram entre 90 e 110% para a maioria dos analitos, os RSDs obtidos foram, em geral, menores que 5% e os limites de detecção ficaram na faixa de 0,7 (Mg) a 71 (Pb) µg L-1. Não foi detectada a presença de As, Co e Pb. As concentrações de Cu e Zn foram semelhantes para as amostras de ciclamato-sacarina e esteviosídeo enquanto as demais espécies mostraram diferenças.

An analytical method for the determination of inorganic species in liquid cyclamate-saccharin and stevioside sweeteners is presented. The method is based on inductively coupled plasma optical emission spectrometry and allowed analysis without prior sample treatment. Instrumental parameters were optimized according to plasma robustness and the signal to background ratio. The accuracy of the method was evaluated for As, Ca, Cd, Co, Cu, Fe, Mg, Mn, Ni, Pb, and Zn employing analyte addition and recovery experiments. The recovery values were between 90 and 110% for the majority of the analytes, the RSDs obtained were, in general, lower than 5% and the limits of detection were in the range 0.7 (Mg) - 71 (Pb) µg L-1. The analyses of different samples indicated that the average values of many of the analytes studied were different for the two types of samples. Copper and Zn concentrations were in the same range and As, Co, and Pb were not detected in any samples.

Inductively Coupled Plasma Optical Emission Spectrometry was used to determine Ca, Mg, Mn, Fe, Zn and Cu in samples of processed and natural coconut water. The sample preparation consisted in a filtration step followed by a dilution. The analysis was made employing optimized instrumental parameters and the results were evaluated using methods of Pattern Recognition. The data showed common concentration values for the analytes present in processed and natural samples. Principal Component Analysis (PCA) and Hierarchical Cluster Analysis (HCA) indicated that the samples of different kinds were statistically different when the concentrations of all the analytes were considered simultaneously.