Investigation of the feasibility to use Zeeman-effect background correction for the graphite furnace determination of phosphorus using high-resolution continuum source atomic absorption spectrometry as a diagnostic tool

The determination of phosphorus by graphite furnace atomic absorption spectrometry at the non-resonance line at 213.6 nm, and the capability of Zeeman-effect background correction (Z-BC) to deal with the fine-structured background absorption due to the PO molecule have been investigated in the presence of selected chemical modifiers. Two line source atomic absorption spectrometers, one with a longitudinally heated and the other with a transversely heated graphite tube atomizer have been used in this study, as well as two prototype high-resolution continuum source atomic absorption spectrometers, one of which had a longitudinally arranged magnet at the furnace. It has been found that Z-BC is capable correcting very well the background caused by the PO molecule, and also that of the NO molecule, which has been encountered when the Pd + Ca mixed modifier was used. Both spectra exhibited some Zeeman splitting, which, however, did not cause any artifacts or correction errors. The practical significance of this study is to confirm that accurate results can be obtained for the determination of phosphorus using Z-BC. The best sensitivity with a characteristic mass of m(0) = 11 ng P has been obtained with the pure Pd modifier, which also caused the lowest background level. The characteristic mass obtained with the mixed Pd + Ca modifier depended on the equipment used and was between m(0) = 9 ng P and m(0) = 15 ng P, and the background signal was higher. The major problem of Z-BC remains the relatively restricted linear working range

Multivariate optimization and validation of an analytical method for the determination of cadmium in wines employing ET AAS

This work describes the optimization and validation of a direct method employing electrothermal atomic absorption spectrometry (ET AAS) for the determination of cadmium in wine. The optimization step was carried out using a two-level full factorial design, involving the followings factors: pyrolysis time (10 s) and temperature (600 ºC), atomization temperature (1300 ºC) and modifier mass (15 µg). Under the optimized conditions, a characteristic mass of 0.7 pg and limits of detection and quantification of 0.030 and 0.100 µg L-1, respectively, were obtained using a sample volume of 20 µL. The precision expressed as relative standard deviation (RSD %) was 0.30, 0.37 and 0.49% for wines with cadmium concentrations of 1.286, 0.266 and 0.356 µg L-1, respectively. The accuracy of the new direct determination methodology applying ET AAS was assessed by comparison with an acid digestion methodology, also with determination by ET AAS, using five wine samples. The proposed method was applied for the determination of cadmium in 30 Brazilian wine samples. The cadmium content varied from 0.146 to 1.563 µg L-1; all these values are lower than the permissible maximum level stipulated by the International Organization of Vine and Wine (OIV) and also by Brazilian legislation, which is 10 µg L-1.O presente trabalho descreve a otimização e validação de um método para determinação direta de cádmio em amostras de vinho por espectrometria de absorção atômica com atomização eletrotérmica (ET AAS). A otimização foi realizada empregando um planejamento fatorial completo de 2 níveis, incluindo os fatores: tempo (10 s) e temperatura de pirólise (600 ºC), temperatura de atomização (1300 ºC) e massa de modificador (15 µg). Sob as condições otimizadas, foi encontrada uma massa característica de 0,7 pg, limite de detecção e quantificação de 0,030 e 0,100 µg L-1, respectivamente, para um volume de amostra de 20 µL. A precisão foi de 0,30, 0,37 e 0,49% (RSD) para amostras de vinho com concentrações de 1,286, 0,266 e 0.356 µg L-1, respectivamente. A exatidão da metodologia de determinação direta empregando ET AAS foi avaliada por comparação usando um método de digestão ácida e determinação também por ET AAS para cinco amostras de vinho. O método foi aplicado para determinação de cádmio em 30 amostras de vinhos brasileiros. A concentração de cádmio variou de 0,146 a 1,563 µg L-1, cujos valores estão abaixo do nível máximo permitido pela Organização Internacional de Vinha e Vinho (OIV) e pela legislação brasileira, 10 µg L-1.788794Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES

Continuum Source Atomic Absorption Spectrometry: Past, Present and Future Aspects - A Critical Review

This review article covers 1½ centuries of history of continuum source atomic absorption spectrometry (CS AAS), starting with the early experiments of Kirchhoff and Bunsen in the 1860s. It also tries to explain why the technique was abandoned in the first half of the 20th century, why it was “re-discovered” in the 1960s in the USA, where several research groups worked intensively on the development of CS AAS for about four decades, and why they finally failed. This review also discusses the major advantages of modern high-resolution CS AAS (HR-CS AAS), which uses a high-resolution double monochromator and a charge coupled device array detector, which adds the wavelength as third dimension to the usual display of absorbance over time. The literature about applications of this technique has been carefully revised. Finally an attempt will be made to foresee future developments of this technique, which is obviously not an easy task.Este artigo de revisão aborda 1½ séculos de história da espectrometria de absorção atômica com fonte contínua (CS AAS), partindo dos primeiros experimentos de Kirchhoff e Bunsen nos anos 1860. Ele também tenta explicar porque a técnica foi abandonada na primeira metade do século XX, porque ela foi redescoberta nos anos 60 nos EUA, onde vários grupos de pesquisa trabalharam intensamente no desenvolvimento da CS AAS por cerca de quatro décadas e, finalmente, não obtiveram sucesso. Esta revisão também discute as principais vantagens da moderna técnica de CS AAS de alta resolução (HR-CS AAS), que usa um monocromador duplo de alta resolução e um detector com arranjo de dispositivos de carga acoplada, o qual adiciona o comprimento de onda como terceira dimensão. A literatura sobre as aplicações de HR-CS AAS foi cuidadosamente revisada. Finalmente, será feita uma tentativa de prever os avanços futuros desta técnica nova e antiga

Determination of triazines in hemodialysis saline solutions by adsorptive stripping voltammetry after extraction in acetonitrile

A method for the voltammetric determination of 2-methylthio-4,6-dialkylamino-1,3,5-triazine (triazines) herbicides in hemodialysis (HD) saline solutions was developed. The herbicides were detected in the saline solutions at the hanging mercury drop electrode (HMDE) with high sensitivities only after extraction of the analytes in acetonitrile (ACN). The salting out effect originated by the saline environment existing in the solutions enabled the extractions. The volume ratio between the saline and ACN phases was investigated in order to find the best sensitivity to detect the triazines. The speciation amongst them (ametryn, desmetryn, prometryn and terbutryn) was not possible. Recoveries between 88 and 107% were calculated in spiked samples, and detection limits of 0.03 mumol L-1 were calculated for the triazines in the saline samples using this methodology