Periodic trends in sensitivity and its dependence on the properties of pyrolytic and non-pyrolytic graphite in graphite-furnace atomic-absorption spectrometry

The sensitivities for metal determination by GFAAS in the peak-height and integration modes were examined with pyrolytic graphite (PG) and non-pyrolytic graphite (NPG) tubes for 34 elements. It was found that there are periodic trends of the mole sensitivity and the elements can be classified according to whether their sensitivity of determination is enhanced by use of (a) the PG tube (alkali, alkaline-earth and transition metals); (b) the NPG tube (semi-metals); about equally by both tubes (Mg, Zn, Cd, and Pb). The mole sensitivity pM for atomic-absorption spectrometry (AAS) was defined as pM = -log(m(h)/A(w)) where m(h) is the weight of an element corresponding to 1% absorption and A(w) is the atomic weight. It was found that the pM values for graphite furnace AAS have a periodic trend similar to that for flame AAS and atomic-fluorescence spectrometry.     

石墨炉原子吸收光谱法测定高温合金中镓

研究了普通石墨管、平台石墨管和涂钼普通石墨管对镓的测定性能.得出涂钼普通石墨管对镓的测定灵敏度和重现性均好于其他石墨管.从而建立了一种更为满意的石墨炉原子吸收测定高温合金中镓的新方法.     

Simultaneous determination of traces in solid samples with laser-AAS

Microamounts of solid samples are vaporized by focused laser radiation (Q-switch ruby). The solid aerosol is transported in an Ar gas stream to a hot graphite tube. The determination of trace metals is made by flameless AAS.A dual channel AA spectrometer is used for the investigation of the reproducibility of the absorbance values in indirect laser AAS. The simultaneous determination of Ag-Mn an Pb-Ag in copper standard metals and in pellets of organic powders show that the inhomogeneity of the materials and differences in the material vaporization by the laser light influence the analytical results.The results of the simultaneous determination of Ag, Al, Mn, Ni. and Pb in different solid samples are compared mutually and with the results of flameless AAS determinations of solutions.     

石墨炉原子吸收法直接测定全血中镉和铅

直接测定人体血镉和血铅较为困难。本文介绍用铂作基体改进剂以提高镉、铅的灰化温度,在灰化阶段除去产生高背景吸收的蛋白,而不发生镉、铅的挥发损失。实现了不需消化样品、络合提取等复杂的化学前处理,用石墨炉原子吸收法和校正曲线直接测定。同时应用衬钽技术,大大延长了石墨管的使用寿命。     

Frequency-modulated simultaneous Atomic Absorption Spectrometry (FremsAAS): Determination of As,Se and Sb

The evaluation of accuracy and efficiency of the frequency-modulated simultaneous Atomic Absorption Spectrometry (FremsAAS) has been extended to an arrangement with EDL as light sources. Fundamental calibrations have been worked out for As, Se and Sb using a graphite furnace as well as hydride generation in combination with a heated quartz tube as atomization unit. The characteristic data are in good agreement with results obtained by conventional single-channel AAS instruments. Determinations in three standard reference materials with different complex matrices resulted in complete agreement with the certified values.     

Frequency-modulated simultaneous Atomic Absorption Spectrometry (FremsAAS): Determination of As, Se and Sb

The evaluation of accuracy and efficiency of the frequency-modulated simultaneous Atomic Absorption Spectrometry (FremsAAS) has been extended to an arrangement with EDL as light sources. Fundamental calibrations have been worked out for As, Se and Sb using a graphite furnace as well as hydride generation in combination with a heated quartz tube as atomization unit. The characteristic data are in good agreement with results obtained by conventional single-channel AAS instruments. Determinations in three standard reference materials with different complex matrices resulted in complete agreement with the certified values.     

Untersuchungen zur atomspektroskopischen spurenanalyse in AIIIBV-halbleiter-mikroproben—V: Bestimmung von selen- und tellurspuren in anorganischen matrices durch aas mit direkter elektrothermischer verdampfung in einer graphitrohrküvette und durch aas im quarzrohratomisator nach hydriderzeugung—untersuchung der matrixeffekte und methodenvergleich

The determination of traces of Se and Te by AAS with generation of volatile hydrides and atomization in a quartz tube, and by AAS with direct electrothermal atomization in a graphite cuvette, is described. The instrumental parameters and the experimental conditions were optimized. For pure acidic solutions it was found best to determine selenium by the hydride technique and tellurium by direct electrothermal atomization. The influence of A^IIIB^V-matrices, and of other substances which also form volatile hydrides, on the determination of Se and Te was investigated. When the hydride technique was used it was found that the main causes of the depression of the AA signals are the formation of insoluble compounds between the matrix and H₂Se or H₂Te, and the loss of NaBH₄ by reaction with reducible compounds. In the case of the graphite cuvette the formation of stable molecules in the plasma and increased light-scattering are the main causes of interference. The analytical possibilities of the methods are compared and the advantages and disadvantages are described.     

Graphite filter atomizer in atomic absorption spectrometry

Graphite filter atomizers (GFA) for electrothermal atomic absorption spectrometry (ETAAS) show substantial advantages over commonly employed electrothermal vaporizers and atomizers, tube and platform furnaces, for direct determination of high and medium volatility elements in matrices associated with strong spectral and chemical interferences. Two factors provide lower limits of detection and shorter determination cycles with the GFA: the vaporization area in the GFA is separated from the absorption volume by a porous graphite partition; the sample is distributed over a large surface of a collector in the vaporization area. These factors convert the GFA into an efficient chemical reactor. The research concerning the GFA concept, technique and analytical methodology, carried out mainly in the author's laboratory in Russia and South Africa, is reviewed. Examples of analytical applications of the GFA in AAS for analysis of organic liquids and slurries, bio-samples and food products are given. Future prospects for the GFA are discussed in connection with analyses by fast multi-element AAS.     

Scanning electron microscopy studies on surfaces from electrothermal atomic absorption spectrometry—I: Polycrystalline electrographite tubes with and without pyrographite coating

Morphological studies on graphite tube surfaces by scanning electron microscopy are presented for unused and corroded tubes from various endurance experiments in electrothermal AAS.Tubes always break in their center as this is the hottest part; tube thinning occurs predominantly at the outside. The inner surface of tubes coated with pyrographite is usually only slightly corroded, unless highly aggressive reagents are applied. Deposition of carbon in thin layers as well as in nodules is observed in the hot central zone.     

石墨炉原子吸收法测定钢铁及合金中微量钒

探讨了石墨炉子吸收法测定钢铁及合金中微量钒的各种实验条件及影响因素。实验表明，采用热解涂层管与光控升温相结合并在温度稳定的情况下原子化，可改善信号峰形，提高灵敏度，消除记忆效应。方法用于钢铁及合金中钒的分析，结果令人满意。     

Analyse von Spurenelementen in biologischen Matrices: Erg?nzende und vergleichende Untersuchungen mit der energiedispersiven R?ntgenfluorescenzanalyse und der Graphitrohrofen-Atomabsorptionsspektrometrie am Beispiel von Fichtennadeln

Ohne Zusammenfassung

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Analysis of trace elements in biological matrices: Supplementary and comparative investigations by energy-dispersive x-ray fluorescence analysis and graphite tube AAS by the example of spruce needles

     

Determination of cadmium,copper and lead in mineral coal using solid sampling graphite furnace atomic absorption spectrometry

Solid sampling graphite furnace atomic absorption spectrometry (SS-GF AAS) was investigated as a potential technique for the routine determination of trace elements in mineral coal and cadmium, copper and lead were chosen as the model elements. Cadmium and lead could be determined at their main resonance lines at 228.8 nm and 283.3 nm, respectively, but an alternate, less sensitive line had to be used for the determination of copper because of the high copper content in coal. No modifier was necessary for the determination of copper and calibration against aqueous standards provided sufficient accuracy of the results. For the determination of cadmium and lead two different modifiers were investigated, palladium and magnesium nitrates in solution, added on top of each sample aliquot before introduction into the atomizer tube, and ruthenium as a ‘permanent’ modifier. Both approaches gave comparable results, and it is believed that this is the first report about the successful use of a permanent chemical modifier in SS-GF AAS. Calibration against solid standards had to be used for the determination of cadmium and lead in order to obtain accurate values. The agreement between the values found by the proposed procedure and the certificate values for a number of coal reference materials was more than acceptable for routine purposes. The detection limits calculated for 1 mg of coal sample using the ‘zero mass response’ were 0.003 and 0.007 μg g⁻¹ for cadmium with the permanent modifier and the modifier solution, respectively, approximately 0.04 μg g⁻¹ for lead, and 0.014 μg g⁻¹ for copper.     

Feasibility of eliminating interferences in graphite furnace atomic absorption spectrometry using analyte transfer to the permanently modified graphite tube surface

A procedure is proposed to avoid spectral and/or non-spectral interferences in graphite furnace atomic absorption spectrometry (GF AAS) by transferring the analyte during the pyrolysis stage from a solid sampling platform to the graphite tube wall that has been coated with a permanent modifier, e.g. by electrodeposition of a platinum-group metal. The direct determination of mercury in solid coal samples was chosen as a model to investigate the feasibility of this idea. The graphite tube surface was coated with palladium and the analyte was transferred from the solid sampling platform to the tube wall at a temperature of 500±50 °C. A characteristic mass of m₀=64 pg Hg was obtained for an atomization temperature of 1300 °C, proposing a quantitative transfer of the analyte to the tube wall. Calibration against aqueous mercury standards was not feasible as this element was lost in part already during the drying stage and could not be trapped quantitatively on the modified graphite tube surface. However, the results for all except one of the coal reference materials were within the 95% confidence interval of the certificate when the slope of a correlation curve between the integrated absorbance, normalized for 1 mg of sample, and the certified value for mercury was used for calibration. A detection limit of 0.025–0.05 μg g⁻¹ Hg in coal, calculated from three times the standard deviation of the investigated coal samples, could be obtained with the proposed method. The spectral interference due to excessive background absorption in the direct determination of mercury in coal could be eliminated completely. It is expected that this analyte transfer can be used in a similar way to eliminate other spectral and/or non-spectral interferences in the GF AAS determination of other volatile analytes.     

Hydride generation AAS performed at 1800–2300°C atomization temperature using a graphite furnace

Summary Mutual interferences of As, Bi, Sb, Se, Sn and Te in the determination of As, Sb, Se and Sn by hydride generation AAS performed at atomization temperatures between 1800 and 2300°C were investigated. The sensitivities for As, Sb and Se were similar to that obtained with a conventional quartz tube, whereas Sn showed a completely different behaviour. Radiotracer experiments indicated that tin was strongly adsorbed on the graphite inlet tube. In processing a typical amount of ca. 50 ng of the element to be determined, the addition of 10–100 g of any of the interfering elements, under the optimized conditions, does not cause a signal depression greater than 12%. In this way, the acceptable concentration range of the interfering elements can be increased by up to three orders of magnitude as compared with the conventional quartz tube technique. However, problems to be solved include reactions of water and hydrogen with heated graphite which give rise to an increased background.     

Speciation of major arsenic species in seawater by flow injection hydride generation atomic absorption spectrometry

Arsenic present at 1 microg L(-1) concentrations in seawater can exist as the following species: As(III), As(V), monomethylarsenic, dimethylarsenic and unknown organic compounds. The potential of the continuous flow injection hydride generation technique coupled to atomic absorption spectrometry (AAS) was investigated for the speciation of these major arsenic species in seawater. Two different techniques were used. After hydride generation and collection in a graphite tube coated with iridium, arsenic was determined by AAS. By selecting different experimental hydride generation conditions, it was possible to determine As(III), total arsenic, hydride reactive arsenic and by difference non-hydride reactive arsenic. On the other hand, by cryogenically trapping hydride reactive species on a chromatographic phase, followed by their sequential release and AAS in a heated quartz cell, inorganic As, MMA and DMA could be determined. By combining these two techniques, an experimental protocol for the speciation of As(III), As(V), MMA, DMA and nonhydride reactive arsenic species in seawater was proposed. The method was applied to seawater sampled at a Mediterranean site and at an Atlantic coastal site. Evidence for the biotransformation of arsenic in seawater was clearly shown.     

Eine mikromethode der flammen-atomabsorptions- und emissions-spektrometrie (platinschlaufen-methode)—I. Die grundlagen der methode—anwendung auf die bestimmung von blei und cadmium in trinkwasser

The paper describes a microanalytical method using flame atomic absorption spectrometry (AAS). The sample is introduced on an electrically heated platinum loop into the flame. This way of sample introduction avoids a nebulizer with its inherent low efficiency; therefore the detection limits of volatile elements are substantially lower than those attained with the conventional flame-AAS method. The determinations of lead and cadmium in drinking water serve as examples which demonstrate that trace analysis with fair precision is feasible in the lower μg/1 range. This range is otherwise accessible only with the graphite tube technique, which is both circumstantial and prone to interferences. The high chemical resistivity of platinum permits several thousand analyses of even strongly acid solutions without perceptible changes of the platinum loop.     

High-Resolution continuum-source atomic absorption spectrometry in an inductively coupled plasma with photodiode array detection

Atomic absorption spectrometry (AAS) is a well established technique using flames and graphite furnaces. An inductively coupled plasma (ICP), however, is an attractive alternative atom/ion reservoir. A high-resolution continuum-source atomic absorption spectrometer with a photodiode array detector and an ICP as the atomization/ionization reservoir is described. Multi-wavelength capability permits the simultaneous determination of several elements by their atomic and/or ionic transitions. Each acquired spectrum is averaged for 10 s to improve the signal-to-noise ratios. Detection limits are calculated for 14 elements and compared with literature values.     

探针-石墨炉原子吸收光谱法测定岩石矿物中的金

本文采用自制探针系统对探针-石墨炉原子吸收光谱法测金的性能,探针系统的制作,探针的处理,探针原子化法的检测限,灵敏度及抗干扰能力进行了详细的研究,探针原子化的各项指标均优于常规的管壁原子化法。采用本法可不必分离基体物质,直接测定地质样品中的金,所得结果与萃取原子吸收法的结果相吻合。     

Coupling of ultrasonic nebulization to flame furnace atomic absorption spectrometry—new possibilities for trace element determination

The use of ultrasonic nebulization (USN) with desolvation system for sample introduction in flame atomic absorption spectrometry (F AAS) and flame furnace atomic absorption spectrometry (FF AAS) with a nickel tube is described. Polytetrafluorethylene (PTFE) adaptors were built to replace the pneumatic nebulizer for USN-F AAS measurements. For USN-FF AAS analysis, an alumina injector allowed the direct introduction of the dry aerosol into the nickel tube. The analytical performance of both systems is shown for Ag, Bi, Cd, Cr, Cu, Mn, Pb, Sb, Se, Tl and Zn. The results demonstrate that a sensitivity gain of up to 39 times can be achieved using USN-FF AAS, mainly due to the increase in residence time and to the absence of dilution of the analyte by the flame gases, as the atomization takes place inside the nickel tube. However, elements that require higher atomization temperatures, such as Cr and Mn, are more efficiently determined using USN-F AAS. To evaluate the accuracy of the proposed methods for the determination of trace elements, five certified reference samples were analyzed, and good agreement was, in general, achieved between certified and determined values at a 95% confidence level. The relative standard deviation was frequently below 5%, demonstrating good precision, particularly for USN-FF AAS. In this sense, coupling of USN with F AAS and especially with FF AAS has proved to be simple, safe, with high precision and good accuracy, also maintaining some of the most important features of F AAS, such as the high analytical frequency and the low running cost.