This study deals with a method for Hg determination in multivitamin supplements. Mercury was extracted with L-cysteine prior to its determination using flow injection-cold vapor generation-inductively coupled plasma-mass spectrometry. A miniaturized flow injection system was employed for Hg vapor generation and its introduction in the plasma whereas 1% (v v-1) HCl and 0.005% (m v-1) NaBH4 were used for that purpose. Mercury extraction was carried out using 6 mL of 1% m v-1 L-cysteine and 50 mg of sample. Accuracy was proved by comparing the Hg concentration found using L-cysteine with the Hg concentration found in the sample decomposed using microwave-assisted digestion, and analysis of certified soil. The limits of detection and quantification of the proposed method were 2 and 6 ng g-1 of Hg, respectively. The relative standard deviation was < 10% (n = 5). Five samples of multivitamin supplements were analyzed and, in any sample, the tolerable amount of Hg (4.0 µg kg-1 body weight) recommended by the World Health Organization was exceeded. The proposed method for Hg determination meets the current legislation and is feasible for Hg monitoring in multivitamin supplements. Lcysteine L cysteine injectioncold cold generationinductively inductively plasmamass mass spectrometry 1 v v1 0005 0 005 0.005 NaBH purpose v- 5 microwaveassisted microwave assisted digestion soil g1 g g- respectively 10 n 5. . 5) 4.0 40 4 (4. kg1 kg kg- weight exceeded 000 00 0.00 4. (4 0.0 ( 0.

Abstract The aim of this study is to analyze the waterborne metal levels in four lakes (one endorheic and three exorheic) of Harmony Point, Nelson Island, Antarctica. Water samples were analyzed by using a quadrupole type inductively coupled plasma mass spectrometer and an inductively coupled plasma optical emission spectrometer. The levels of As, Cu, Mn, Mo, and V were significantly lower and those of Cr, Mg, Na, and Sr were significantly higher in the endorheic lake than in the other lakes. Most water samples presented levels of Ag, Be, Cd, Pb, Se, Tl, and U below the limit of quantification, while for Ba, Co, and Ni around half of the samples were below this limit. The waterborne metal levels were not significantly different between the exorheic lakes. Waterborne metal levels in the freshwater lakes from Harmony Point did not show any clear relationship with their levels in the soil of the region or with bird guano, and overall, their levels indicate an environment without anthropogenic influence. Apparently, the Na levels are influenced by salt spray from the ocean, as they are related to the distance of the lakes from the ocean. one Island Antarctica As Cu Mn Mo Cr Mg Ag Be Cd Pb Se Tl quantification Ba Co guano overall influence Apparently ocean

A solid sampling electrothermal vaporization inductively coupled plasma optical emission spectrometry (ETV-ICP OES) method for determination of As, Cd, Cr, Cu, Mn, Mo, Ni, Pb, Pd, Pt, Rh, Ru and V in pharmaceuticals is proposed. Tricyclic pharmaceuticals were directly analyzed due to their difficult decomposition with acids. Pyrolysis and vaporization temperature, sample mass, and reaction gas (Freon) flow rate were evaluated. The effect of organic and inorganic compounds was evaluated for matrix matching. The limits of detection ranged from 0.04 µg g−1 (Cu) to 107 µg g−1 (As) and the relative standard deviation was lower than 10%. The investigated elements were not detected in the analyzed samples with the exception of Cr in cyclobenzaprine hydrochloride. Since there was no certified reference materials available for metals and metalloids in pharmaceuticals, the accuracy of the method was evaluated by an independent technique and by analyte recovery. Inductively coupled plasma mass spectrometry was employed for analyte determination after sample decomposition by microwave induced combustion. The agreement of the results found by both techniques was better than 87% and analyte recoveries ranged from 91 to 103%.

A pirohidrólise foi utilizada no preparo de amostras de carbeto de silício (SiC) para posterior determinação de B usando espectrometria de emissão óptica com plasma indutivamente acoplado (ICP-OES) e espectrometria de massa com plasma indutivamente acoplado (ICP-MS). Parâmetros importantes como temperatura, fluxo de água e ar, tempo de reação e uso de V2O5 foram avaliados. Adicionalmente, foi avaliada a interferência de W sobre as linhas de emissão de B durante as determinações por ICP-OES. A exatidão foi avaliada usando material de referência certificado (CRM BAM S003) e valor de bias inferior a 1% foi encontrado entre os valores de referência e obtido experimentalmente. Limite de detecção (LOD) de 0,010 μg g−1 foi obtido usando pirohidrólise e determinação por ICP-MS. A pirohidrólise é um método de preparo de amostras simples que permitiu a utilização de água deionizada como solução absorvedora para a determinação de B em SiC.

Pyrohydrolysis was used for sample preparation of silicon carbide (SiC) and subsequent determination of B using inductively coupled plasma optical emission spectrometry (ICP-OES) and inductively coupled plasma mass spectrometry (ICP-MS). Important parameters for pyrohydrolysis method as temperature, air and water flow rates, reaction time and use of V2O5 were evaluated. In addition, a study of W spectral interference on B emission lines was evaluated for ICP-OES determination. Accuracy was evaluated using certified reference material (CRM BAM S003) and bias value lower than 1% between the certified and determined value was achieved. Limit of detection (LOD) of 0.010 μg g−1 was obtained using pyrohydrolysis and ICP-MS. Pyrohydrolysis is a very simple sample preparation method that allowed the use of deionized water as absorbing solution for B determination in SiC.

A method based on pyrohydrolysis was proposed for cement sample preparation and further chloride determination by spectrophotometry using flow injection analysis. Analytical parameters were evaluated and, under the selected conditions, the calibration curve was linear in the range of 0.2 to 10.0 µg mL-1 with r2 = 0.998. The limit of detection was5 µg g-1 of chloride and the relative standard deviation was less than 7%. The proposed pyrohydrolysis method is relatively simple and can be used for sample preparation for further spectrophotometric determination of low concentrations of chloride in cement.

A determinação de fluoreto por eletrodo íon seletivo (ISE) em nanotubos de carbono (CNTs) é proposta após a decomposição por piroidrólise. Até 1 g de amostra pode ser decomposta, obtendo-se assim baixos limites de detecção (1,5 μg g-1), boa precisão (RSD < 5%) e exatidão (concordância maior do que 95% com os valores dos materiais de referencia certificados (CRMs) e combustão iniciada por microondas (MIC)). O fluoreto é absorvido em água e a solução resultante pode ser analisada diretamente por ISE. A pirohidrólise é simples de ser executada e não requer instrumentação sofisticada, sendo bastante atrativa para controle de fluoreto em NTCs em análises de rotina.

Fluoride determination by ion selective electrode (ISE) in carbon nanotubes (CNTs) is proposed after pyrohydrolysis decomposition. Up to 1 g of CNTs could be decomposed improving the limit of detection (1.5 μg g-1), precision (RSD < 5%) and accuracy (agreement higher than 95% with values of certified reference materials (CRMs) and microwave-induced combustion (MIC)). Fluoride could be absorbed in water and the resulting solution can be analyzed by ISE. Pyrohydrolysis is easy to be performed and does not require any sophisticated instrumentation, which is attractive for routine fluoride control in CNTs.

Neste trabalho foi utilizada a piroidrólise para a decomposição de suplemento mineral utilizado na nutrição animal, para a posterior determinação de F, Br e I. Flúor foi determinado por potenciometria utilizando eletrodo íon-seletivo para fluoreto, enquanto que Br e I foram determinados por espectrometria de massa com plasma indutivamente acoplado. Os principais parâmetros que influenciam a piroidrólise foram investigados e, após a devida avaliação dos mesmos, foram fixadas as seguintes condições: a temperatura do reator em 1000 °C durante 10 min; a proporção entre a massa de amostra e a massa de acelerador em 1 + 5 e a vazão do gás carreador em 200 mL min-1. A exatidão do método foi avaliada usando teste de recuperação do analito e análise de materiais de referência certificados de rocha fosfática e de solo. O método foi aplicado para análise de suplemento mineral. Os limites de quantificação foram de 16, 0,3 e 0,07 µg g-1 para F, Br e I, respectivamente. Assim, usando-se um método relativamente simples e de baixo custo é possível a decomposição de até 5 amostras por hora. Portanto, a piroidrólise pode ser usada como um método de rotina para o preparo de amostra de suplemento mineral para a determinação de F, Br e I.

Pyrohydrolysis was employed for mineral supplements decomposition prior to F, Br and I determination. Fluoride determination was carried out by potentiometry using a fluoride-ion selective electrode, whereas Br and I were determined by inductively coupled plasma mass spectrometry. The main parameters that influence on pyrohydrolysis were investigated. After evaluation, the following conditions were established: reactor temperature of 1000 ºC during 10 min; sample plus accelerator mass ratio of 1 + 5 and carrier gas (air) flow rate of 200 mL min-1. The accuracy of the proposed method was evaluated by analyte recovery tests and analysis of certified reference materials of phosphate rock and soil. Commercial mineral supplement samples were analyzed. The limits of quantification were 16, 0.3 and 0.07 µg g-1 for F, Br and I, respectively. By using a relatively simple and low cost pyrohydrolysis system up to 5 samples can be processed per hour. The developed sample preparation procedure can be routinely employed for F, Br and I determination in mineral supplements.

O aumento da escala de produção agropecuária e agroindustrial traz, como consequência, a necessidade por alternativas para a mitigação dos impactos ambientais. As cadeias produtivas de proteína animal (ex.: suinocultura, bovinocultura e avicultura) produzem efluentes com elevada concentração de compostos nitrogenados. Neste contexto, o processo ANAMMOX (do inglês Anaerobic Ammonium Oxidation) se constitui em uma nova estratégia de alto desempenho visando remover compostos nitrogenados de águas residuárias, agropecuárias e agroindustriais, sob condições quimiolitoautotróficas. Este artigo apresenta uma revisão bibliográfica de trabalhos publicados nos últimos 15 anos sobre estudos deste processo, discutindo sua rota metabólica, demonstrando os micro-organismos envolvidos e os parâmetros de controle do processo, além de estudos desenvolvidos no Brasil e possíveis aplicações.

The increase in agriculture and agro-industrial scale production brings the necessity for alternatives to mitigate environmental impacts. The animal protein production chains (e.g. swine, cattle and poultry) produce effluents with high concentration of nitrogen compounds. In this context, the ANAMMOX (Anaerobic Ammonium Oxidation) process is a new strategy for nitrogen removal in a high rate from agricultural and agro-industrial wastewaters under chemolithoautotrophic conditions. This paper presents a literature review of papers published in the last 15 years about the ANAMMOX process, discussing their metabolic pathway, microorganisms, main control parameters as well as studies conducted in Brazil and application possibilities.

A determinação de Al, Cd, Co, Cr, Cu, Mg, Mn e Pb em nanotubos de carbono (CNTs) foi realizada por espectrometria de absorção atômica com atomização eletrotérmica e amostragem direta de sólidos (DSS-ET AAS, corretor de fundo com fonte de deutério). Foram avaliados os parâmetros de aquecimento, uso de Pd como modificador químico, possibilidade de calibração com soluções aquosas e massa máxima de amostra. Para comparação dos resultados as amostras foram analisadas por espectrometria de massa com plasma indutivamente acoplado (ICP-MS) e espectrometria de emissão óptica com plasma indutivamente acoplado (ICP OES) após decomposição por via úmida em sistema de alta pressão assistida por micro-ondas e também por combustão iniciada por micro-ondas. Não foram observadas diferenças significativas entre os resultados obtidos pelo método proposto e pelas outras técnicas. A exatidão também foi avaliada por comparação com resultados de análise por ativação neutrônica (NAA). A calibração foi possível com soluções de referência aquosas. Os sinais de fundo foram sempre inferiores a 0,02 (altura de pico) e o uso de modificador químico não foi necessário. O método proposto possibilitou a determinação de todos os analitos, com menores limites de detecção quando comparados com as outras técnicas.

Metal impurities (Al, Cd, Co, Cr, Cu, Mg, Mn and Pb) were determined in carbon nanotubes (CNTs) by direct solid sampling electrothermal atomic absorption spectrometry (DSS-ET AAS, deuterium lamp background corrector). Parameters as pyrolysis and atomization temperatures, use of Pd as chemical modifier, feasibility of calibration using aqueous standard solutions and maximum sample mass were investigated. Results obtained by the proposed method were compared with those obtained by neutron activation analysis (NAA) and also by inductively coupled plasma mass spectrometry (ICP-MS) and inductively coupled plasma optical emission spectrometry (ICP OES) after high-pressure microwave assisted wet digestion and microwave-induced combustion methods. No significant differences were observed between the results obtained by DSS-ET AAS, ICP-MS and ICP OES after both digestion methods and also by NAA. Calibration was performed using aqueous standards. Background signals were always lower than 0.02 (peak height) and no chemical modifier was used. The proposed method allowed the determination of all elements in CNTs with lower limits of detection in comparison with other techniques.

Um método para determinação de arsênio em BaSO4 por espectrometria de absorção atômica com aquecimento eletrotérmico e introdução de amostras sólidas (SoS-ET AAS) é descrito. Foram avaliados dois sistemas de correção de fundo (BG), deutério e efeito Zeeman (Z). Com o uso combinado de hidrogênio e Pd o BG foi diminuído. Resultados exatos e precisos foram obtidos usando Z-SoS-ET AAS. O desvio padrão relativo usando Z-SoS-ET AAS foi menor que 9,5%. O limite de detecção foi 0,005 μg g-1 e a massa característica foi 25,4 pg. Os resultados foram comparados com os obtidos usando o método de preparo de amostras sugerido pela Farmacopeia Europeia, com determinação usando espectrometria de emissão ótica e espectrometria de massas, ambos com plasma indutivamente acoplado, porém os resultados foram cerca de 20% menores. Vantagens como simplicidade, elevada frequência de determinações e boa exatidão foram obtidos em comparação com o método descrito na farmacopeia.

A method for arsenic determination in pharmaceutical grade BaSO4 by solid sampling electrothermal atomic absorption spectrometry (SoS-ET AAS) is described. Two background (BG) correction systems, deuterium and Zeeman-effect (Z), were evaluated. Background was decreased by using hydrogen combined with Pd. Accurate and precise results were obtained using Z-SoS-ET AAS. Relative standard deviation using Z-SoS-ET AAS was lower than 9.5%. Limit of detection was 0.005 μg g-1 and characteristic mass was 25.4 pg. Results were also compared with those obtained using the preparation method suggested by European Pharmacopoeia for BaSO4 followed by determination using inductively coupled plasma optical emission spectrometry and inductively coupled plasma mass spectrometry. Results were around 20% lower than results obtained using the proposed method. Some advantages as simplicity, higher sample throughput were found when compared with the official method currently described in pharmacopoeia.

Pyrohydrolysis is proposed for fossil fuels sample preparation for further fluorine and chlorine determination. Samples were heated during 10 min at temperatures up to 1000 °C. Water vapor was passed through the reactor and the volatile products were condensed and collected in NH4OH solution. Fluoride was determined by potentiometry using an ion selective electrode (ISE) and Cl by ICP OES and DRC-ICP-MS. The results are in good agreement with certified values and the precision is better than 10% (n = 4). Sample preparation by means of pyrohydrolysis is relatively simple, whereas chlorine and fluorine can be determined at low concentrations.

Um sistema de combustão iniciada por microondas foi acoplado a um espectrômetro de absorção atômica com atomização em tubo metálico aquecido com chama (FF) do tipo ar-acetileno para a determinação de cádmio em sangue. Amostras de sangue liofilizado foram preparadas como comprimidos, posicionadas em um suporte de quartzo e introduzidas em uma câmara de vidro empregada para a etapa de combustão. A câmara foi acoplada ao tubo metálico usando tubos de politetrafluoroetileno e de quartzo. A ignição foi iniciada por irradiação microondas usando solução de nitrato de amônio adicionada em papel previamente descontaminado. Oxigênio foi usado na etapa de combustão e para o transporte dos produtos gerados até o tubo aquecido. Grafite em pó de alta pureza foi misturada com as amostras antes do preparo dos comprimidos. O volume da solução de NH4NO3, a vazão de oxigênio, a estequiometria da chama, o tipo de suporte e a quantidade de massa de amostra foram avaliados. A calibração foi possível usando solução de referência adicionada a comprimidos de grafite de alta pureza, não sendo necessário o uso de material de referência certificado (CRM). Foi possível a combustão de até 56 µg de amostra, permitindo a obtenção de limite de quantificação de 0,018 µg g-1 e massa característica de 50 pg de Cd. Os valores dos brancos foram baixos (absorbância integrada menor que 0,01 s). Os resultados foram considerados satisfatórios com respeito à exatidão (concordância com valores de CRMs entre 95 e 99%) e à precisão (coeficiente de variação < 12%). Até 15 determinações podem ser feitas por hora incluindo a etapa de pesagem.

Microwave-induced combustion system was coupled to a metallic flame furnace (FF) atomic absorption spectrometer and applied for cadmium determination in blood. Lyophilized blood samples were prepared as pellets, positioned on a quartz holder and introduced into a glass chamber used for the combustion step. The glass chamber was coupled to the metallic flame furnace by using polytetrafluoroethylene and quartz tubes. Ignition was performed by microwave radiation using ammonium nitrate solution added to a small piece of previously cleaned paper. Oxygen was used to assist the sample combustion and also to transport combustion products up to the FF heated by an air/acetylene flame. High purity graphite powder was mixed with samples before pellets preparation. The volume of NH4NO3 solution, oxygen flow-rate, flame stoichiometry, sample holder type and the sample mass range were evaluated. Calibration step was feasible using adsorbed reference solution in pelletized high purity graphite avoiding the use of certified reference material (CRM). Sample masses up to 56 µg could be used allowing quantification limit of 0.018 µg g-1 and characteristic mass of 50 pg Cd. Low values for blanks were obtained (integrated absorbance lower than 0.01 s) and results were considered satisfactory regarding to both accuracy (agreement with results using CRMs between 95 to 99%), and precision (relative standard deviation < 12%). Up to 15 determinations can be performed per hour including the weighing step.

Foi desenvolvido um sistema em linha para a especiação de Hg orgânico (Hg org) e Hg inorgânico (Hg inorg) em chorume. Clorocomplexos produzidos a partir do Hg inorg são separados em uma coluna trocadora de ânions. O Hg retido na coluna é eluído com NaBH4 na presença de HCl. O Hg0 produzido é medido por espectrometria de absorção atômica com geração de vapor frio (CV AAS). O Hg org, que não fica retido na coluna, é misturado com NaBH4 produzindo espécies voláteis de Hg, as quais são amalgamadas numa rede de Au/Pt. O Hg é removido desta coluna por aquecimento a 600 °C e medido por CV AAS. Para a especiação de Hg inorg e Hg org em chorume, as amostras são centrifugadas, filtradas e tratadas com HCl. Os limites de detecção (3 s) são 9 e 12 ng L-1 de Hg para Hg inorg e Hg org, respectivamente. A freqüência de análise é 22 h-1.

This work deals with on line speciation of organic Hg (Hg org) and inorganic Hg (Hg inorg) in urban landfill leachate. Chlorocomplexes of Hg inorg are produced in HCl medium and retained on an anion exchange column. The retained Hg is eluted with NaBH4 in presence of HCl. Hg0 is produced and then measured by cold vapor atomic absorption spectrometry (CV AAS). Hg org does not interact with the resin and is mixed with NaBH4 at the exit of the column producing volatile species of Hg that are then amalgamated by a gauze of Au/Pt. Mercury is removed from the gauze by heating to 600 °C and subsequently measured by CV AAS. For Hg inorg and Hg org speciation in urban landfill leachate, the samples are centrifuged, filtered and treated with HCl. The detection limits (3 s) of Hg inorg and Hg org are 9 and 12 ng L-1 of Hg, respectively. The analysis frequency is 22 h-1.

Este estudo teve por objetivo avaliar o metabolismo do flúor (F) em ovinos. Para tanto, utilizaram-se 12 animais, com cinco meses de idade, os quais receberam como dieta base 3% do peso vivo de feno de alfafa e água ad libitum. Os animais foram divididos e constituíram um grupo Controle, que recebeu apenas sal iodado (5g de NaCl/animal + 0,2mg I/kg matéria seca) e, um grupo Tratado, que recebeu sal iodado adicionado de fluoreto de sódio (4,7mg F/kg de peso corporal). Esses sais foram administrados via sonda oro-esofágica, diariamente por um período de 150 dias. Para análise de F, coletaram-se amostras de sangue, urina e fezes e, ao fim do período experimental, após a eutanásia dos animais, coletou-se a glândula pineal e amostras de osso. Também nesta ocasião, coletou-se uma amostra de rim para exame histopatológico. Analisando-se os teores séricos, urinários e ósseos de F, verificou-se que foram significativamente superiores nos animais Tratados em relação aos Controles. Quanto ao F contido na glândula pineal, não houve diferença significativa entre os grupos. Na análise histológica do rim, não foram observadas alterações. Conclui-se que a administração crônica de flúor induz ao acúmulo desse elemento nos ossos, mesmo havendo um alto teor de cálcio na alimentação e esse acúmulo parece não ser nocivo aos animais. Em ovinos, a capacidade orgânica de acúmulo ósseo e excreção urinária do flúor é diferente de outras espécies animais.

The objective of the present study was to evaluate fluorine metabolism in growing lambs. Twelve 5-month-old male lambs maintained on alfalfa hay (3% BW) and non-fluorinated water ad libitum were used. Animals were allocated into Control, receiving 5g NaCl/animal/day + 0.2mg I/kg dry matter) and Treated group, receiving the same treatment plus sodium fluoride (4.7mg F/kg body weight). Mineral treatment was given by gavage, daily for 150 days. Blood, urine and fecal samples were collected during and the end of the experiment. At the end of treatment period animals were euthanized and kidney, pineal and bone samples were collected. Urine F was higher in treated animals throughout the experiment. Bone F levels were also increased in treated animals; pineal F content however, was not different between groups. Kidney histology revealed no differences. It is concluded that chronic F administration induces accumulation of the element in the skeleton. However such fact appears not to be detrimental to animals. Rates of F accumulation in bone and urine excretion obtained in other species can not be used in growing lambs.

Um novo sistema para análise direta de amostras sólidas por espectrometria de absorção atômica com chama é proposto como alternativa para a determinação de elementos traço em carvão. Para a demonstração do potencial do procedimento a determinação de manganês foi investigada. Amostras de carvão foram moídas e pesadas diretamente em recipientes de polietileno e transportadas na forma de um aerossol seco até uma cela de quartzo posicionada entre o feixe óptico e a base do queimador. Sinais transientes foram totalmente integrados em 1 segundo. A influência das condições operacionais sobre os sinais foi estudada. Sinais de fundo foram sempre baixos e uma massa característica de 1,9 ng Mn foi encontrada. Os resultados foram considerados satisfatórios com respeito à exatidão (entre 97,5 e 103,2%) e precisão (RSD melhor que 6%). O sistema proposto é simples e pode ser facilmente adaptado a espectrômetros comerciais, permitindo a análise de mais de 80 amostras por hora.

A new device for the direct solid analysis by flame atomic absorption spectrometry was investigated as an alternative technique for the determination of trace elements in coal. The potential application of the proposed procedure for the determination of manganese was investigated. Ground coal test samples were weighed directly into polyethylene vials and carried as a dry aerosol to a slotted quartz vaporization cell placed between the flame burner and optical path. The transient signals obtained were totally integrated in 1 second. The effect of operating conditions on the analytical signal was investigated. Background signals were always low and a Mn characteristic mass of 1.9 ng was found. Results were considered satisfactory regarding to both accuracy (between 97.5 and 103.2%) and precision (RSD better than 6%). The proposed system is simple and can be easily adapted to any conventional atomic absorption spectrometers allowing the analysis of more than 80 test samples in an hour.