Determination of trace impurities in titanium dioxide by direct solid sampling electrothermal atomic absorption spectrometry

A true direct solid sampling electrothermal atomic absorption spectrometry method with Zeeman-effect background correction (Analytik Jena ZEEnit 60 AAS) was developed for the determination of As, Cd, Hg, Pb, Sb and Zn in powdered titanium dioxide of pharmaceutical, food and cosmetics grade. The interaction of the titanium matrix and graphite surface of the sample carrier boat in a transversely heated graphite tube atomizer was investigated. Conversion of titanium dioxide to interfering TiO₂–TiC-liquid phase, running out the sampling boat, was observed at temperatures above 2000 °C. The temperature program was optimized accordingly for these volatile analytes in atomization and cleaning steps in order to prevent this interference and to prolong significantly the analytical lifetime of the boat to more than one thousand runs. For all elements, calibration by aqueous standard addition method, by wet-chemically analyzed samples with different content of analytes and/or by dosing one sample in different amounts, were proved as adequate quantification procedures. Linear dynamic calibration working ranges can be considerably expanded up to two orders of magnitude within one measurement run by applying three-field dynamic mode of the Zeeman background correction system. The results obtained by true direct solid sampling technique are compared with those of other independent, mostly wet-chemical methods. Very low limits of detection (3σ criterion) of true solid sampling technique of 21, 0.27, 24, 3.9, 6.3 and 0.9 ng g^− 1 were achieved for As, Cd, Hg, Pb, Sb and Zn, respectively.     

APDC沉淀分离富集石墨炉原子吸收测定海水和生物样品中铅,镉,钴,铜,锡,砷和钼

我们曾研究一种新的分离富集方法,即在酸性水溶液中加入吡咯烷二硫代甲酸铵(APDC)沉淀镍后,将Ni-PDC溶于甲基异丁酮(MIBK)中,有机相直接进样石墨炉原子吸收测定尿和生物样品中痕量镍.本工作将此方法扩大应用于海水和生物样品中铅、镉、钴、铜、锡、砷和钼     

Application of analyses on the basis of characteristic mass: Determinations of indium, silver and thallium in drainage sediment and geochemical samples

When Pd and EDTA ammonium salt are used as a common matrix modifier, the establishment of a common furnace programme for the determinations of indium, silver and thallium would greatly simplify routine analysis. The continuous determination of indium, silver and thallium by the analyses on the basis of characteristic mass and the graphite furnace with the V-shaped boat is described. The possibility of the proposed method for application to continuous determination of indium, silver and thallium in real sample is discussed. The continuous determination of indium, silver and thallium in drainage sediment and geochemical samples by the analyses on the basis of characteristic mass is carried out and the results of sample analyses are in good agreement with the expected values.     

Direct determination of cadmium and copper in seawater using a transversely heated graphite furnace atomic absorption spectrometer with Zeeman-effect background corrector

Methods for the direct determination of copper and cadmium in seawater were described using a graphite furnace atomic absorption spectrometer (GFAAS) equipped with a transversely heated graphite atomizer (THGA) and a longitudinal Zeeman effect background corrector. Ammonium nitrate was used as the chemical modifier to determine copper. The mixture of di-ammonium hydrogen phosphate and ammonium nitrate was used as the chemical modifier to determine cadmium. The matrix interference was removed completely so that a simple calibration curve method could be applied. This work is the first one with the capability of determining cadmium in unpolluted seawater directly with GFAAS using calibration curve based on simple aqueous standards. The accuracy of the methods was confirmed by analysis of three kinds of certified reference saline waters. The detection limits (LODs), with injection of a 20-mul aliquot of seawater sample, were 0.06 mug l(-1) for copper and 0.005 mug l(-1) for cadmium.     

Determination of phosphorus in steel with a stabilized-temperature graphite furnace and zeeman-corrected atomic absorption spectrometry

The determination of phosphorus in steel by graphite furnace a.a.s. is plagued by a spectral interference from the iron matrix which results in overcompensation when a continuum-source background corrector is used. Zeeman background correction using an alternating transverse magnetic field at the furnace eliminates this problem and allows a routine determination of phosphorus down to 0.002% in steel. Lanthanum is an effective matrix modifier for the phosphorus determination, but its enhancing effect depends largely upon the tube material used and the sample matrix. A 0.2% lanthanum solution was found to be optimum. The stabilized-temperature platform furnace concept allows an interference-free determination of phosphorus in steel, down to 0.002%, directly against aqueous standards. Atomizing the sample from a pyrolytic graphite platform in an uncoated graphite tube provides the optimum environment for a phosphorus determination.     

Determination of heavy metals in environmental reference materials using solid sampling graphite furnace AAS

Summary Cadmium and nickel are determined in Coal, Coal Fly Ash and Urban Particulate Matter Reference Materials using solid sampling graphite furnace AAS. The evaluation of integrated absorbance is required to overcome the effect of the matrix on the rate of atomization. The homogeneity of the samples under investigation in the range between 0.3 mg and 1.5 mg sample weight is good enough to make possible relative standard deviations around 10% for cadmium and between 10 and 20% for nickel. Cadmium can be determined against reference solutions, the nickel results are slightly lower than the certified value if calibration is performed against aqueous solutions. Calibration against a solid reference is therefore recommended. Less sensitive resonance lines and an internal gas flow through the tube are required for some of the samples to keep the absorbance in the linear calibration range. The direct determination of chromium in these samples is hampered by the lack of less sensitive resonance lines. Due to high concentrations of chromium in the samples, direct determination without dilution of the sample e.g. by spectrally pure graphite powder is impossible. The peak for the refractory carbide forming element vanadium is strongly suppressed by the Coal and the Urban Particulate matrix. Integration of the signal within a reasonable time and at an atomization temperature of 2650 °C is impossible.

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Bestimmung von Schwermetallen in Umwelt-Referenzmaterialien mit Hilfe der Feststoff-Graphitrohrofen-AAS

     

Determination of vanadium in water by atomic absorption spectrometry with electrothermal atomization and using hot injection and preconcentration on the graphite tube

A sensitive method for the determination of vanadium in water by atomic absorption spectrometry with electrothermal atomization and using hot injection and preconcentration on the graphite tube is described. The water sample (200 μl) is added to the heated graphite tube in four portions over 200 s. Magnesium nitrate is used as matrix modifier. The precision, accuracy and interferences of the method were investigated. The method allows vanadium down to 0.27 μg l^?1 to be detected.     

Rapid determination of 2,3,7,8-tetrachlorodibenzo-p-dioxin in water samples by using solid-phase microextraction followed by gas chromatography with tandem mass spectrometry

A rapid and simple method of using solid-phase microextraction was developed for determination of 2,3,7,8-tetrachlorodibenzo-p-dioxin (2,3,7,8-TCDD) in water samples. In this method, the target analyte is extracted from the sample into the polymeric coating of the fused-silica fiber. After exposure, the fiber is thermally desorbed in the heated injection port of the gas chromatograph, and a chromatographic analysis is performed by using low-resolution tandem mass spectrometry. Parameters that may affect the extension of the microextraction process, such as sampling mode, sample volume, temperature, agitation, and sampling time, were studied. Extraction efficiencies for 3 coating fibers were investigated: 100 microm poly(dimethylsiloxane) (PDMS), 65 microm PDMS-divinylbenzene, and 75 microm carboxen-PDMS. Linearity was evaluated (R = 0.999) for a 250-fold concentration range from the fg/mL to the pg/mL level. The 2,3,7,8-TCDD was detected at the fg/mL level when the headspace over the water sample was sampled for 60 min; the limit of detection obtained was better than that of Method 8280B of the U.S. Environmental Protection Agency. The proposed method performed well when applied to the analysis of tap water, lake water, and seawater samples.     

Optimization of the determination of selenium in marine samples by atomic absorption spectrometry: Comparison of a flameless graphite furnace atomic absorption system with a hydride generation atomic absorption system

A comparison has been made between a graphite furnace system based on nickel as a matrix stabilizing metal and an automated hydride generation system with a heated quartz cell. The effect of nickel as a matrix modifier was studied in pure selenite solutions as well as in biological matrixes by different charring temperatures. The suppression effect of different acids on the response of the analyte is reported and discussed. The use of an electrically heated quartz tube as an alternative to the argon hydrogen flame method unproved the selenium determination by hydride generation atomic absorption. The effect of hydrochloric acid to secure quantitative formation of selenium (IV) and the interference of copper in the response measurements have been studied. Further a comparison has been made between three different digestion procedures when the hydride generation atomic absorption system was applied. The results of the graphite furnace atomic absorption and the hydride generation atomic absorption were found to be equally accurate, but the graphite furnace technique gave better reproducibility.     

固体进样一直接测汞仪法测定金精矿粉中微量汞

将金精矿粉样品直接置于石英舟中,在高纯氧气氛中燃烧,释放出汞,与齐化管中的金形成金汞齐,于900℃热释放出汞蒸汽,用直接测汞仪法测定汞的含量。测定结果的相对标准偏差为0．28％～1．57％（n=6）,方法检出限为1．0pg／kg,加标回收率为95．7％～117．4％。用该法对4种土壤标准样品进行了测定,测定结果与标准值相符。该方法适合于金精矿粉中微量汞的测定。     

Analysis of high purity graphite and silicon carbide by direct solid sampling electrothermal atomic absorption spectrometry

Solid sampling electrothermal atomic absorption spectrometry using the boat technique and a transversely heated graphite tube was applied to direct analysis of graphite and silicon carbide powders for 14 and 12 impurity elements, respectively. With graphite, for all analytes under investigation, a very effective in-situ analyte/matrix separation was achieved. That was the case also for analytes in silicon carbide requiring atomization temperatures below 2400 degrees C. At higher atomization temperatures, the decomposition products of silicon carbide give rise to significant background, which can still be corrected. Sample amounts of up to 4 mg graphite and 8 mg silicon carbide per analysis cycle were applied. For all analytes in both materials, limits of detection at the lower ng g(-1) and sub-ng g(-1) level were achieved, excluding arsenic for which they were 50 ng g(-1) and 23 ng g(-1) for graphite and silicon carbide, respectively. Quantification was performed using calibration curves measured with aqueous standard solutions. The accuracy was checked by comparison of the results with those obtained by instrumental neutron activation analysis and by other independent methods.     

固体进样-冷原子吸收法测定食用明胶中的微量汞

样品直接置于石英舟中,在高纯氧气氛中燃烧,释放出的汞与齐化管中的金形成金汞齐,于900℃加热释放出汞蒸气,用冷原子吸收法测定汞的含量。方法的检出限为0.003 ng,测定结果的相对标准偏差为1.13%(n=6),加标回收率为90.5%~97.0%,并用标准样品对方法进行了确证。该方法具有良好的精密度与准确度,适用于明胶中微量汞的测定。     

Preconcentration of trace silver with yeast for river water analysis

A new preconcentration method with yeast is presented. The method was evaluated for the determination of trace silver in river waters by graphite furnace atomic absorption spectrometry (GFAAS). A suitable cultivation bed for preconcentration of silver was 1.75 mg ml-1 2-ammonium hydrogen phosphate. The optimal cultivation time and temperature were 2 h and 25 degrees C. Under optimal conditions, silver in aqueous sample was concentrated to 6.9-fold by yeast. The detection limit was 4.6 pg ml-1 (3S/N) for silver in river water. The yeast preconcentration method was applied to the determination of silver in river waters. The recovery of spiked silver was in the range of 89 to 110%. By the preconcentration, it was found that ultra trace silver in river waters could be determined without interferences of matrix elements, after only the cultivation and with no chemical treatment.     

Investigation of thallium hydride generation using in situ trapping in graphite tube by atomic absorption spectrometry

Thallium hydride was generated from aqueous solutions by merging sample and sodium tetrahydroborate reductant in a batch system. In situ preconcentration of volatile thallium hydride in a preheated graphite furnace coated with palladium, which was used as both the collection medium and atomizer, greatly improved the sensitivity for the determination of thallium by hydride generation atomic absorption spectrometry. The presence of tellurium can increase the generation efficiency of thallium hydride. The operating conditions were optimized. The calibration graph is linear up to 100 ng and the characteristic mass for thallium was 0.92 ng which is seventeen times lower than that obtained with the heated quartz tube atomizer.     

Determination of trace elements in seawater samples by on-line column extraction/graphite furnace atomic absorption spectrometry

An innovative procedure for the on-line coupling of ion chromatography with graphite furnace atomic absorption spectrometry is described, which is particularly effective for the determination of trace metals in seawater samples. The Capillary Injection Device (CID) is used as an interface which allows the eluent to be transferred from the chromatographic column into the graphite tube at a flow rate of as high as 2 ml/min. The analytical procedure is based on the metal complex formation with 8-hydroxyquinoline in the sample solution, followed by the preconcentration of the complexes in a chromatographic column packed with XAD-2 resin. The complexes were then eluted from the column with methanol, and quantitatively injected into the furnace. The procedure was validated by determining cadmium and lead in certified reference seawater samples at a level of 30–40 pg/g, with a typical reproducibility of 10% and an accuracy of better than 5%. Finally, it was tested on a real sample of seawater. Due to the high reproducibility, a pg/g concentration level can be measured.     

Determination of copper and nickel in vegetable oils by direct sampling graphite furnace atomic absorption spectrometry

The quality of food products has been receiving great attention due to its influence on human nutrition and health. In this sense, the determination of trace metals in foods has turned an important field on food analysis. Concerning vegetable oils, its metal trace composition is an important criterion for the assessment of their quality once it is known that trace metals affect their rate of oxidation, influencing freshness, keeping properties as well as storage. In the present work an analytical method which enables the direct determination of Cu and Ni in vegetable oils by graphite furnace atomic absorption spectrometry (GFAAS), using a “solid” sample strategy is presented: in nature, samples are directly weighed on the graphite platform boat and inserted in the graphite tube. An adequate temperature program permitted the calibration by external aqueous analytical curves. Good concordance between the proposed procedure and EPA procedures was found in the analysis of real samples. Limits of detection of 0.001 and 0.002 μg g⁻¹ were found for Cu and Ni, respectively, in the original samples, and they were comfortably below the concentrations found.     

Simultaneous determination of germanium,arsenic, tin and antimony with total-reflection X-ray fluorescence spectrometry using the hydride generation technique for matrix separation—first steps in the development of a new application

This paper introduces a new perspective for total-reflection X-ray fluorescence analysis (TXRF), that is the simultaneous determination of Ge, As, Sn and Sb in seawater. As is well known from atomic absorption spectroscopy (AAS) and inductively coupled plasma techniques (ICP) compounds of these elements can be reduced by sodium borohydride to their hydrides and thus separated from the matrix. In this work the hydride generation is used for matrix separation in TXRF measurements. For this purpose the following procedures are considered: (1) Preconcentration of hydrides by absorption in solvents, and evaporation of some μl of this solution on the sample carrier. (2) Decomposition of hydrides in a heated thin silica tube, or at rough and/or catalytically active surfaces, e.g. in adequately prepared columns, eluting of the species by acid and evaporation of some μl of this solution on the sample carrier. (3) Decomposition of hydrides directly on the surface of a heated silica sample carrier as a thin amorphous film. (4) Combustion of hydrides in the hydrogen flame and deposition of an elemental film on the sample carrier. Basically, all four ways have been tested and the results are promising. © 1997 Elsevier Science B.V.     

Determination of ultra-trace levels of gold in size-segregated atmospheric particulate samples by laser induced fluorescence: towards an aerosol tracer

A method is described for measuring the gold content of integral and size-segregated samples of atmospheric particulate matter. After acid digestion and a liquid/ liquid extraction, the sample are analysed by Two-Colour Laser Induced Fluorescence in a graphite furnace. An absolute instrumental detection limit of 1 fg is achieved. Assuming a sampled volume of 1 m(3), this corresponds to an atmospheric concentration of 50 fg m(-3). Due to blank limited noise, the above limits increase to 20 fg and 1 pg m(-3), respectively. Results of the analysis of filter samples as well as of size-segregated impactor samples are presented.     

Determination of Ultratrace Amounts of Copper and Cadmium in Seawater by Graphite Furnace Atomic Absorption Spectrometry with Flow-Injection Semi On-line Preconcentration

Methods are described for the determination of ultratrace amounts of copper and cadmium in seawater by graphite furnace atomic absorption spectrometry with flow-injection, microcolumn preconcentration. A new type of C₁₈ column loaded with sodium diethyldithiocarbamate (sodium-DDC) was used to extract copper and cadmium from seawater as the DDC chelates. The analytical effects of the pH of the mixture of the sample and sodium-DDC solutions and the concentration of the chelating reagent were studied. Sodium-DDC-loaded columns and unloaded C₁₈ columns with different shapes and volumes were compared. To determine copper in seawater, a simple aqueous calibration was made with a mixture of palladium and magnesium nitrate as a matrix modifier, while for cadmium no matrix modifier was necessary. This method required only small seawater volumes, 600 and 400 μl for the determination of copper and cadmium respectively, with preconcentration factors of 15-fold for copper and 10-fold for cadmium. Detection limits for the preconcentration of aqueous solutions of copper and cadmium were 0.024 and 0.004 μg liter⁻¹ (3σ), respectively. Results for determinations of copper and cadmium in National Research Council of Canada, CASS-2, Nearshore Seawater Reference Material showed no significant differences between the certified values and the measured values, based on Student′s t test at the 95% confidence level. The relative standard deviations of the various measurements varied between 2 and 8%.     

Electrothermal vaporization system using furnace-fusion technique for the determination of lead in botanical samples by inductively coupled plasma atomic emission spectrometry

A new approach to sample digestion, subsequent vaporization and introduction into an inductively coupled plasma atomic emission spectrometer was developed for the direct determination of lead. To each small sample cuvette made of tungsten, a mixture of a ground solid sample and powdered diammonium hydrogenphosphate was precisely weighed. The cuvette was positioned onto the tungsten boat furnace (TBF) incorporating a vaporizer. Tetramethylammonium hydroxide solution was added. Then the cuvette was heated and maintained at a wet-digestion temperature to decompose the solid sample. After digestion, the temperature was elevated to generate the analyte vapor for introduction into a plasma. Since the solid samples were wet-digested in the sample cuvettes before vaporization, they could be analyzed by using a calibration curve prepared from aqueous standard solutions. This method was applied to the determination of lead in several biological materials with satisfactory results.