A procedure for partial digestion of bovine tissue is proposed using polytetrafluoroethylene (PTFE) microvessels inside a baby-bottle sterilizer under microwave radiation for multi-element determination by inductively coupled plasma optical emission spectrometry (ICP OES). Samples were directly weighed in laboratory-made polytetrafluoroethylene vessels. Nitric acid and hydrogen peroxide were added to the uncovered vessels, which were positioned inside the baby-bottle sterilizer, containing 500 mL of water. The hydrogen peroxide volume was fixed at 100 mu L The system was placed in a domestic microwave oven and partial digestion was carried out for the determination of Ca, Cu, Fe. Mg, Mn and Zn by inductively coupled plasma optical emission spectrometry. The single-vessel approach was used in the entire procedure, to minimize contamination in trace analysis. Better recoveries and lower residual carbon content (RCC) levels were obtained under the conditions established through a 2(4-1) fractional factorial design: 650 W microwave power, 7 min digestion time, 50 mu L nitric acid and 50 mg sample mass. The digestion efficiency was ascertained according to the residual carbon content determined by inductively coupled plasma optical emission spectrometry. The accuracy of the proposed procedure was checked against two certified reference materials. (C) 2009 Elsevier B.V. All rights reserved.
In this present work a method for the determination of Ca, Fe, Ga, Na, Si and Zn in alumina (Al(2)O(3)) by inductively coupled plasma optical emission spectrometry (ICP OES) with axial viewing is presented. Preliminary studies revealed intense aluminum spectral interference over the majority of elements and reaction between aluminum and quartz to form aluminosilicate, reducing drastically the lifetime of the torch. To overcome these problems alumina samples (250 mg) were dissolved with 5 mL HCl + 1.5 mLH(2)SO(4) + 1.5 mL H(2)O in a microwave oven. After complete dissolution the volume was completed to 20 mL and aluminum was precipitated as Al(OH)(3) with NH(3) (by bubbling NH(3) into the solution up to a pH similar to 8, for 10 min). The use of internal standards (Fe/Be, Ga/Dy, Zn/In and Na/Sc) was essential to obtain precise and accurate results. The reliability of the proposed method was checked by analysis of alumina certified reference material (Alumina Reduction Grade-699, NIST). The found concentrations (0.037%w(-1) CaO, 0.013% w w(-1) Fe(2)O(3), 0.012%w w(-1)Ga(2)O(3), 0.49% w w(-1) Na(2)O, 0.014% w w(-1) SiO(2) and 0.013% w w(-1) ZnO) presented no statistical differences compared to the certified values at a 95% confidence level. (C) 2011 Elsevier B.V. All rights reserved.; Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP); Fundacao de Amparo a Pesquisa do Estado de Sao Paulo (FAPESP); Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq); Conselho Nacional de Desenvolvimento Cientifico e Tecnologico (CNPq)
O objetivo deste estudo foi avaliar parâmetros para o desenvolvimento de métodos visando à determinação elementar em alumina, cimento e quartzo por espectrometria de emissão óptica com plasma indutivamente acoplado (ICP OES) com amostragem de suspensão. Alguns elementos foram investigados como possíveis candidatos a padrões internos (PIs) Be, Dy, Gd, In, La, Sc, Y, Yb eTl. Amostras de material de referência certificado (CRM) de alumina (Alumina Reduction Grade 699), de cimento Portland (1889a Blended with Limestone e 1886a White Portland cement with low iron) do National Institute of Standard and Technology (NIST), e amostras de quartzo, cedidos pelo Departamento de Física da Universidade Federal de São Carlos (UFSCar), denominados T-4FI, T-2FI e T-4GR, foram utilizadas na otimização instrumental, no desenvolvimento e na avaliação da exatidão do método. Nanopartículas de sílica de alta pureza (Wacker HDK® T40), Wacker Chemie AG foram utilizadas no estudo de adsorção dos elementos e padrões internos como proposta de produção de material calibrante para a análise direta de sólidos. Para a escolha dos PIs foram construídos gráficos de correlação usando valores de potenciais de excitação, energias de ionização e temperaturas de fusão dos analitos e dos candidatos a PIs. Análise exploratória por agrupamentos hierárquicos (HCA) e análise dos componentes principais (PCA)...
O objetivo deste estudo foi avaliar parâmetros tais como, moagem, tamanho de partículas, homogeneidade, segregação, dissolução de amostras e amostragem de suspensão, visando o desenvolvimento de método para a determinação de Ir, Pd, Pt e Rh por espectrometria de emissão óptica com plasma indutivamente acoplado (ICP OES) em sílica mesoporosa para uso catalítico. Após a moagem em moinho eletrônico de almofariz e pistilo, a análise do tamanho e distribuição das partículas revelou que 89% das partículas apresentam tamanhos <100 µm e 23% com tamanho <5 µm. Na avaliação de segregação dos analitos na amostra, os resultados obtidos para amostra com moagem grosseira, indicaram que os elementos estão distribuídos de maneira heterogênea entre as frações. Entretanto, a moagem fina aumentou a homogeneidade e esta pode ser uma etapa importante e necessária no sentido de evitar segregação da amostra. A análise por difração e de Raios-X mostrou que não ocorreram reações mecanoquímicas durante a moagem e por fluorescência de Raios-X forneceu resultados discrepantes entre os laboratórios, o pode estar relacionado com a heterogeneidade que induziu erros de amostragem. A avaliação de desempenho do ICP OES foi feita a partir do estabelecimento de parâmetros de mérito como seletividade...
A combustão iniciada com micro-ondas (MIC) foi aplicada para decomposição de amostras de tabaco de cigarro e subsequente determinação de bromo e cloro por espectrometria de emissão óptica com plasma indutivamente acoplado (ICP OES). Massas de amostra de até 500 mg foram decompostas em frascos fechados e pressurizados com 20 bar de oxigênio. A combustão foi completada em menos de 30 s e os analitos foram absorvidos em solução diluída de (NH4)2CO3. A exatidão foi avaliada usando materiais de referência certificados e mediante a determinação utilizando ICP-MS. A concordância foi melhor do que 98% usando 50 mmol L-1 de (NH ) CO 4 2 3 como solução absorvedora e 5 min de refluxo. A temperatura durante a combustão foi superior a 1400 °C e o conteúdo de carbono residual nos digeridos após MIC foi menor que 1%. Até oito amostras podem ser decompostas simultaneamente. Limites de quantificação utilizando MIC e determinação por ICP OES foram de 12 e 6 µg g-1 para Br e Cl, respectivamente.; The microwave-induced combustion (MIC) was applied for cigarette tobacco samples digestion and further determination of bromine and chlorine by inductively coupled plasma optical emission spectrometry (ICP OES). Samples masses up to 500 mg were combusted in closed vessels using 20 bar of oxygen. Combustion was complete in less than 30 s and analytes were absorbed in diluted (NH4)2CO3 solution. Accuracy was evaluated using certified reference materials with similar matrix composition and comparison with results obtained using ICP-MS. The agreement was better than 98% using 50 mmol L-1 (NH4)2CO3 as absorbing solution and 5 min of reflux. Temperature during combustion was higher than 1400 °C and the residual carbon content in digest obtained after MIC was lower than 1%. Up to eight samples could be processed simultaneously and a single absorbing solution was suitable for both Br and Cl. Limit of quantification by MIC and further ICP OES determination was 12 and 6 μg g-1 for Br and Cl...
This study deals with the development of a method for As, Bi, Cd and Pb preconcentration and determination using cloud point extraction (CPE) and inductively coupled plasma optical emission spectrometry (ICP OES). Hydride generation, pneumatic nebulization and micronebulization/aerosol desolvation were investigated for introducing the surfactant rich phase into the ICP. O,ODiethyldithiophosphate (DDTP) was used as complexant and octylphenoxypolyethoxyethanol (Triton X-114) as surfactant. The influence of concentration of HNO3, HCl, DDTP, Triton X-114, surfactant rich phase in methanol, reductant of As, and NaBH4 was evaluated. The enrichment factors obtained were 10, 18, 12 and 14 for As, Bi, Cd and Pb, respectively. The limits of detection (LODs) of As, Bi, Cd and Pb were 0.055, 0.063, 0.047 and 0.28 mg L 1, respectively. Precision and accuracy were assessed by analysis of certified enriched water (NIST 1643e), oyster tissue (NIST 1566b), tobacco leaves (CTAOTL- 1), bush branches and leaves (GBW 07602) and analyte spiking. Microwave-induced combustion (MIC), sonication, and acid digestion were used for sample preparation. The developed method was applied for extraction and determination of As, Bi, Cd and Pb in river water, wine, fertilizer and urine. Analyte recovery close to 100% and relative standard deviation (RSD) lower than 5% were observed.
The brown alga Pilayella littoralis was used as a new biosorbent in an on-line metal preconcentration procedure in a flow-injection system. Al, Co, Cu and Fe were determined in lake water samples by inductively coupled plasma optical emission spectrometry (ICP-OES) after preconcentration in a silica-immobilized alga column. Like other algae, P. littoralis exhibited strong affinity for these metals proving to be an effective accumulation medium. Metals were bound at pH 5.5 and were displaced at pH < 2 with diluted HCl. The enrichment factors for Cu-II, Fe-III, Al-III and Co-II were 13, 7, 16 and 11, respectively. Metal sorption efficiency ranged from 86 to 90%. The method accuracy was assessed by using drinking water certified reference material and graphite furnace atomic absorption spectrometry (GFAAS) as a comparison technique. The column procedure allowed a less time consuming, easy regeneration of the biomaterial and rigidity of the alga provided by its immobilization on silica gel. (C) 2003 Elsevier B.V. All rights reserved.
The feasibility of Portland cement analysis by introduction of slurries in an inductively coupled plasma optical emission spectrometer (ICP-OES) with axial viewing has been evaluated. After a fast manual grinding of the cement samples, owing to the pulverized state of this material, 0.1% m/v slurries were prepared in 1% v/v HCl. The calibration was performed adopting two strategies: one based on slurries prepared from different masses (50, 75, 100 and 125 mg) of a Portland cement standard reference material (NIST SRM 1881), and the other one based on aqueous reference solutions. A complete analysis of cement for major (Al, Ca, Fe, Mg and Si), minor and trace elements (Mn, P, S, Sr and Ti) was accomplished. Both strategies led to accurate results for commercial Portland cement samples, except for Si and Ti. for which the calibration with aqueous reference solutions resulted in low values. Applying a paired t-test it was shown that most results were in agreement at a 95% confidence level with a conventional fusion decomposition procedure. The ICP-OES with axial viewing and end-on gas configuration for removal of the recombination plasma zone was effective for cement slurry analysis without any undesirable particle deposition in the pre-optics interface and without severe spectral interferences. (C) 2002 Elsevier B.V. B.V. All rights reserved.
Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP); Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES); Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq); L-proline was immobilized on controlled pore glass to study the ability of this material for the separation and preconcentration of Sb(III) and Sb(V). The substrate was packed in a minicolumn and incorporated in a flow injection system. The effluents of the on-line solid phase extraction (before and after elution) were directly coupled to the hydride generation inductively coupled plasma optical emission spectrometry system. The effect of pH, sample (and eluent) volume, flow rates of sample loading and elution on separation of Sb(III) e Sb(V) were evaluated. Our experiments demonstrated that Sb(V) was not retained and it was selectively determined during the loading step, while retained Sb(III) was determined afterelution. The proposed system was also used for the selective preconcentration of Sb(III). In this case, a preconcentration factor of 11 and a limit of detection of 90 ng L-1 for Sb(III) were achieved when 8 mL of sample were loaded into the column. The speciation analysis of inorganic Sb in river water and effluent samples was performed using the proposed method. The values obtained for total Sb (obtained by sum of Sb(III) and Sb(V)) were in good agreement with expected values. Recoveries of Sb(III) and Sb(V) in the river water Standard Reference Material 1640 (from National Institute of Standard and Technology) and spiked river waters were between 83 and 111%. (C) 2008 Elsevier B.V. All rights reserved.
A determinação de elementos metálicos em alimentos ricos em açúcar é um desafio analítico devido a interferência da matriz. Diluições das amostras podem minimizar este efeito, por outro lado, podem reduzir as concentrações dos elementos metálicos abaixo do limite de detecção. Assim, o pré-tratamento é usualmente necessário para destruir ou transformar a matriz orgânica e extrair os íons metálicos ligados aos complexos orgânicos buscando, ainda, minimizar os resíduos gerados nas etapas de preparação e análise química. Este trabalho descreve diferentes tratamentos de amostras de mel, como a digestão ácida, fotólise oxidativa e digestão enzimática, alternativas ¿limpas¿ no preparo de amostras para a determinação de Mn, Cd, Pb, Zn, Ba, Cu, Co, Fe, Al, Cr, Ni e As por ICP OES Espectrometria de Emissão Óptica em Plasma de Argônio com Acoplamento Indutivo. Os resultados obtidos com os diferentes tratamentos foram avaliados levando em consideração o tempo, facilidade de operação e desempenho dos parâmetros analíticos. O método de fotólise oxidativa mostrou-se viável para a análise deste tipo de amostra uma vez que os resultados analíticos mostraram exatidão e precisão adequadas, além de não gerar resíduos químicos no final do tratamento. O fator custo também foi favorável a este tratamento...
A flow injection system coupled to focused microwave-assisted oven was used for on-line orange juice sample digestion for determination of Ca, Cu, Fe, K, Mg, Mn, Na, P, and Zn by inductively coupled plasma optical emission spectrometry. The reactor coil was a PTFE tube (4.0 m long and 1.6 mm i.d.) positioned into the commercial glass tube of the focused microwave oven. Aliquots of 500 muL of sample and 1000 muL of reagent (80% v/v HNO3) were mixed in a confluence and carried out to the reactor coil by air carrier. The relative standard deviation for five replicates of sample was lower than 5.0%. Good recoveries varying from 91 to 111% were obtained for added concentrations of the interest elements. The results obtained using the proposed digestion system are in agreement with those obtained for total digestion at the 95% confidence level. With this on-line digestion system was possible to carry out 12 samples h-1, minimizing contamination, saving consumption of samples and reagent and low residue generation.
The developed work investigated the application of mechanochemical synthesis for promoting reactions in the samples and for synthesizing new compounds for increment of emission intensities of analytes in clays and refractory materials slurries in inductively coupled plasma optical emission spectrometry with axial viewing. The hypothesis is that it is possible to generate more volatile compounds during the grinding step and these new compounds will increase the intensities of emission signals for slurries introduced in the plasma. The action of two chemical modifiers, LiBO2 and Na2CO3, added during the grinding step was evaluated. The clays and refractory materials mixed with the chemical modifier were ground for 2 h using a high impact ball mill with a tungsten carbide grinding container and balls. Slurries were prepared by dispersing the modified clays and refractory materials in 10% v v-1 HNO3 solution and by shaking them in an ultrasonic bath to ensure good dispersion. The compounds produced during the grinding step were characterised by X-ray diffraction and thermogravimetric analysis. Both techniques indicated the formation of new compounds in clays and refractory materials by mechanochemical synthesis. Chemical modification effects were evaluated by changes of the emission intensities of Al...
Preparative methods for quantification of inorganic constituents in honey by Inductively Coupled Plasma Optical Emission Spectrometry (ICP OES) using microwave assisted digestion and ultrasonication procedures were developed. Analytical aspects such as matrix complexity, instrumental optimization and the essentiality/toxicity of the species K, Ca, Mg, Na, Fe, Mn, Zn, Cu, Co, Ni, Pb, Cd were considered. Parameters such as plasma power, nebulizer flow rate, torch configuration and the convenience of the use of yttrium as internal standard were evaluated. Recoveries between 93 and 107% (microwave digestion) and between 90 to 110% (ultrasonication procedure) and relative standard deviations lower than 10% were obtained. Samples of Brazilian honeys, from different parts of the country, were analysed and the results obtained provide relevant information about their mineral content.
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.
Generation of volatile species (CVG) from Fe2+, Fe3+, Cr3+, CrO4²ˉ, Mn2+ and MnO4ˉ ions by reaction with NaBH4 reductant in HCl, CH3COOH and citric acids using gas-liquid phase separation system and inductively coupled plasma atomic emission spectrometry detection (ICP OES) was reported. The optimized conditions were obtained using low concentrations of HCl (0.05‑0.075 mol L‑1) and NaBH4 (0.25-1.0% (m/v)). Volatile species were more effectively generated for lower oxidation state of the analytes. Detection limits of 10, 25 and 66 ng mL-1 were achieved for Mn2+, Fe2+ and Cr3+, respectively.
The presence of some inorganic elements in biodiesel can compromise the fuel quality and enhance the emission of pollutants. In this context, a new procedure for biodiesel sample preparation using a high pressure asher (HPA) is presented, aiming the determination of Al, Ca, Cu, Fe, K, Mg, Mn, Na, Ni, P, Sr, and Zn, in soybean, sunflower, animal fat, cotton and castor oil, by inductively coupled plasma optical emission spectrometry (ICP OES). The digestion conditions of the HPA were optimize to digest 1.5 g of biodiesel, with HNO3 and H2O2, at a temperature of 300 °C and pressure of 435 psi, which considered the sample dilution factor, the total solids in solution and the acidity for ICP OES determinations. Analytes concentrations in these biodiesels were calculated using standard addition method. Detection limits from 0.05 to 0.7 mg kg- 1 were suitable to attend biodiesel quality parameters, government policy and legislations worldwide. Therefore, the proposed procedure proved to be efficient to eliminate the major organic interferences typically present in oil based samples allowing a fast, precise, interference-free and robust analytical condition for biodiesel characterization.
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%.
This thesis aims to explore simple methods to improve the analytical performance of inductively coupled plasma (ICP) optical emission spectrometry (OES) and mass spectrometry (MS).
1. An argon-nitrogen mixed-gas plasma with a hydrogen sheath gas was developed in order to improve plasma robustness for the analysis of geological/environmental samples by ICP-MS and ICP OES. Nitrogen was added to the outer plasma gas, to reduce matrix effects, while hydrogen was added as a sheath, around the nebulizer flow, to improve energy transfer to the central channel. Increased robustness allowed for the direct quantitative multi-element analysis of certified soil, ore and seawater reference materials by ICP-MS and ICP OES, without using any matrix matching or internal standardization.
2. An IR-heated sample introduction system with a conventional pneumatic nebulizer was investigated in order to improve the analytical performance of ICP OES. The aerosol generated by a pneumatic nebulizer, coupled to various spray chambers, was heated to 230 °C using an IR heater. Under optimum conditions and compared to conventional pneumatic nebulization at room temperature, a 6-fold improvement in sensitivity and a 4 to 7-fold improvement in detection limit was obtained for 38 elements using the IR-heated sample introduction setups. Another IR-heated sample introduction system was also investigated for both aqueous and organic (metals-in-oil) solutions. Under optimum conditions and compared to conventional pneumatic nebulization at room temperature...
The direct analysis of solid samples by electrothermal vapourization (ETV) coupled to inductively coupled plasma (ICP) optical emission spectrometry (OES) is typically reserved to niche applications. This thesis is focused on a new niche application: geochemical exploration. First, solid sampling (SS) ETV-ICP-OES was used to determine the distribution of elements in soil samples in the Flin Flon-Snow Lake terrain, Manitoba, Canada in order to locate the undercover ore deposit. Samples were first vaporized by ETV and the vapor was then introduced into the ICP.
Under optimal conditions and with a four-step ETV temperature program, the surface distribution of some pathfinder elements in soils showed obvious anomalies delineating the undercover ore. External calibration with 0–4 mg of soil reference material, together with internal standardization with an argon emission line, yielded results for Zn and P in good agreement with those obtained, following aqua regia (AR) digestion, by ICP mass spectrometry (MS).
The vertical distribution of target elements in soil samples from the same area was also determined, which revealed anomalously high concentrations toward the surface of the profile in the area above the undercover ore. Again...
A variety of sunscreen products have been developed to afford the consumer protection against some of the deleterious effects, for example erythema, caused by solar ultraviolet radiation. The requirement that suncare products offer broad-spectrum protection has resulted in the use of inorganic oxides, such as micronized titanium dioxide (TiO2), in their formulation. However, there are now concerns about the photocatalytic effects of the TiO2 in these products and its potential phototoxicity to the skin through the generation of reactive oxygen species such as hydroxyl and superoxide anion radicals. It is important, therefore, that the amounts of TiO2 in suncare products be closely monitored and maintained within stipulated ranges. A simple, fast and reliable analytical method for the determination of TiO2 in commercial sunscreen products by inductively coupled plasma-optical emission spectrometry (ICP-OES) was developed and validated. The limits of detection and quantitation were found to be 0.018 and 0.062mL-1, respectively. The average percentage recovery of TiO2 was 102.32 ± 2.87 % with a RSD of 2.81 %. The method was applied to determine the concentration of TiO2 in 22 commercial suncare samples of which 14 contained TiO2. The amounts of TiO2 measured in these sunscreens ranged from 0.05 to 3.21 %. To our knowledge this is the first study that reports the amounts of TiO2 in sunscreen products available on the South African market.