Electrothermal atomic-absorption and atomic-fluorescence spectrometry with a tungsten-coil atomizer

A pulsed electrothermal atomizer of the tungsten-coil type and apparatus for its application in atomic-absorption and atomic-fluorescence spectrometry are described. A tungsten-coil atomizer is shown to be just as good as commercial electrothermal atomizers with regard to sensitivity and reproducibility, but to have better operating characteristics. A theoretical model for formation of the atom cloud is given. Mechanisms for atomization of different groups of element in an atmosphere of pure argon and in the presence of reductants (hydrogen and carbon) are proposed.     

Trace metal analysis of rocks by flameless atomic-absorption spectrometry with a metal micro-tube atomizer

Flameless atomic-absorption spectrometry with a metal micro-tube atomizer has been studied. The element to be determined was atomized by electrical heating of the micro-tube in an inert atmosphere within a glass chamber. A detailed study of the atomic-absorption characteristics of the micro-tube atomizer is presented. The absolute sensitivities were 2.6 x 10(-12), 2.9 x 10(-11), 2.5 x 10(-10), 1.1 x 10(-10) and 1.4 x 10(-10)g for copper, cobalt, aluminium, palladium and selenium, respectively. The interferences of cations were studied for determination of cobalt and copper. Cobalt and copper in rock samples were determined in order to evaluate the metal micro- tube atomizer.     

Electrothermal atomic-absorption spectrophotometric determination of molybdenum

The sensitivity for determining Mo by ETA-AA is dependent on the heating programme employed when the peak-height method is used, but not when the peak area is used for evaluation of the AA signals. The linear range is greater at lower heating rate. Molybdenum can be directly determined in up to 8% NaCl solution without chemical pretreatment or background correction by making use of the high ashing temperature allowed, at which the matrix NaCl can be totally removed. The minimum recovery is 94.5%. Amounts of alkaline earth metals greater than 4000 times the amount of Mo give scatter signals, but these are time-resolved from the Mo signal. Any small effect on the peak height or area can be compensated for by background correction. The interference of tungsten is significant even at low concentrations (2-5 mug/ml) owing to the formation of stable compounds. Mo is determined in brines and acid digests of phosphate rocks after preconcentration and separation with the APDC-MIBK system, by ETA-AA of the organic extracts with or without mineralization.     

Electrothermal atomization of calcium and strontium in a molybdenum micro-tube

The excitation and ionization of calcium and strontium in a molybdenum micro-tube atomizer and their use in atomic-absorption spectrometry are described. Increasing hydrogen flow led to complex calcium atomization profiles for absorption measurements, but decreasing hydrogen flow resulted in higher atomic emission. Ionization of calcium and its suppression by potassium were also observed. Strontium was measured effectively by atomic absorption because of the higher sensitivity. Increasing hydrogen flow resulted in a lower atomization temperature and higher absorption for strontium, while decreasing hydrogen flow resulted in higher atomic emission. No interference from 100-fold amounts of magnesium, calcium and sodium was found for atomization of strontium, but 100-fold amounts of aluminium shifted the peak temperature for strontium though with no variation of appearance temperature and peak absorption. A small shift in peak temperature was observed for strontium in the presence of 100-fold amounts of phosphate.     

Electrothermal atomization with a metal micro-tube in atomic absorption spectrometry

The processes of atom formation and dissipation in a molybdenum micro-tube atomizer have been studied to obtain information on the reaction involved. Vapor temperature was found to be close to atomizer surface temperature. Appearance temperatures and activation energies were obtained for Al, Co, Cu, Mn, Pb, Sb, Se, Sn and Te in argon and argon-hydrogen atmospheres. The atom formation processes are divided into two groups : the reduction of the metal oxide followed by the atomization of free metal, and thermal dissociation of the metal oxide. Hydrogen significantly changes atom formation processes for some metals compared to those in pure argon. The dissipation process of atoms from the micro-tube atomizer appears to be purely gas-phase diffusional.     

Selective determination of antimony(III) and antimony(V) with ammonium pyrrolidinedithiocarbamate, sodium diethyldithiocarbamate and dithizone by atomic-absorption spectrometry with a carbon-tube atomizer

The extraction behaviour of antimony(III) and antimony(V) with ammonium pyrrolidinedithiocarbamate, sodium diethyldithiocarbamate and dithizone in organic solvents has been investigated by means of frameless atomic-absorption spectrophotometry with a carbon-tube atomizer. The selective extraction of antimony(III) and differential determination of antimony(III) and antimony(V) have been developed. With ammonium pyrrolidinedithiocarbamate and methyl isobutyl ketone, when the aqueous phase/solvent volume ratio is 50 ml/10 ml and the injection volume in the carbon tube is 20 mul, the sensitivity for antimony is 0.2 ng/ml for 1% absorption. The relative standard deviations are ca. 2%. Interferences by many metal ions can be prevented by masking with EDTA. The proposed methods have been applied satisfactorily to determination of antimony(III) and antimony(V) in various types of water.     

The determination of lead and nickel by atomic-absorption spectrometry with a flameless wire loop atomizer

In an extension of studies of flameless atomizers for atomic-absorption spectrometry, an electrically heated tungsten-rhenium alloy wire loop was examined. Reduction of metallic salts to ground-state metal atoms was accomplished with the high temperature produced by the loop. Lead and nickel were investigated. Experimental parameters such as wavelength, slit width, atomization temperature and sheathing gas flow rate were optimized. Absolute detection limits of 6.6·10^?10 and 1.2·10^?10, and absolute sensitivities of 7·10^?10 and 8·10^?11 g of lead, were established for unenclosed and enclosed cells, respectively. The interferences of twenty cations and sixteen anions were studied; foreign cations generally enhanced the lead absorption by retarding its vaporization, allowing the slow detection system to respond more efficiently. Nickel was investigated as a representative less volatile metal; an absolute detection limit of 1.6·10^?9 and an absolute sensitivity of 9·10^?10 g of nickel were established.     

Electrothermal atomization atomic absorption spectrometry of cadmium with a platinum tube atomizer

The determination of cadmium by electrothermal atomization atomic absorption spectrometry with a platinum tube atomizer in the presence of air has been investigated. The detection limit of cadmium was 0.09 pg (9 pg/ml for a 10-mul volume). The relative standard deviation of the measurement was 2.9%. For 2.5 pg of cadmium, Cu, Pb, Zn, Al, Ca, Fe, K, Mg and Na (10(4)-10(5)-fold) did not interfere with the absorption signal. The method has been applied to the determination of cadmium in some biological materials. The average analytical value found for the standards lay within the limits of the certified values. The remarkable merits of the platinum atomizer are its stability in air and long life-time (able to withstand more than 1000 heating cycles in air).     

Ultratrace molybdenum determination in biological samples by graphite-furnace atomic-absorption spectrometry

A method is described for molybdenum determination in human serum at sub-ng/ml levels by graphite-furnace atomic-absorption spectrometry. Sample preparation involves a nitric acid digestion, chelation with benzohydroxamic acid and extraction into hexanol. A detection limit of 0.1 ng/ml and a characteristic concentration of 0.18 ng/ml for 1% absorption can be achieved. The effectiveness of the method has been demonstrated by analysis of unspiked and spiked human serum, standard reference materials, and comparison with the results obtained by inductively-coupled plasma atomic-emission spectroscopy.     

Electrothermal atomization of arsenic,antimony and thallium using a graphite atomizer with refractory metal platforms

The electrothermal atomization of the volatile elements arsenic, antimony and thallium from a refractory metal platform consisting of a tungsten coil and/or a refractory metal foil with the dimensions of a conventional graphite platform was studied. Several combinations of refractory metal platforms were investigated, as follows: W platform; Ta platform; W coil; W coil on a W platform and W coil on a Ta platform. The best combination for these elements as regards both thermal stabilization and sensitivity is the W coil on a Ta platform. Thermal stabilization is also achieved with a W coil on a W platform. The presence of Pd-containing chemical modifier favors the thermal stabilization of the analytes. The sufficient amount is 2 micrograms of Pd. The maximal temperatures of pyrolysis are higher (arsenic, antimony) or equal (thallium) to those when using different chemical modifiers, added as solutions. It may be concluded, that the refractory metal platforms act as "built-in modifiers". They are suitable for the determination of arsenic, antimony and thallium in samples of complex matrix composition where high thermal stability of the analytes during the pyrolysis step is required.     

Electrothermal atomic-absorption spectrometry of arsenic and its application to environmental samples

Electrothermal atomization of arsenic with a metal micro-tube atomizer has been studied. Thiourea and thionalide were found to give effective atomization of arsenic. A method involving extraction of the thionalide complex for determining traces of arsenic in water and soil is described.     

Simple method for determination of selenium in biological materials by flameless atomic-absorption spectrometry using a carbon-tube atomizer

A method for determination of selenium in biological materials by flameless atomic-absorption spectrometry using a carbon-tube atomizer is described. The sample is burned by an oxygen-flask combustion procedure, the resulting solution is treated with a cation-exchange resin to eliminate interfering cations, the selenium is extracted with dithizone in carbon tetrachloride and the resulting selenium dithizonate is combined with nickel nitrate in the carbon tube to enhance the sensitivity for selenium and avoid volatilization losses. The method measures selenium concentrations as low as 0.01 mug/g with a relative standard deviation of 8%.     

Influence of volatile hydride-forming elements on antimony determination by atomic-absorption spectrometry with hydride-generation

A study was undertaken to determine the interfering effects of arsenic, bismuth, germanium, lead, selenium, tin and tellurium on trace determination of antimony by atomic-absorption spectrometry with hydride-generation. A 1% NaBH(4) solution was used as reductant and a small amount of oxygen was added to the hydrogen produced, to support the combustion and atomization of SbH(3). The interference from selenium in the determination of antimony is removed if potassium iodide-ascorbic acid solution or copper sulphate is added to the sample solution. The interference of tin and tellurium can also be avoided by adding potassium iodide-ascorbic acid solution. A possible interference mechanism is discussed.     

Mechanism of cobalt atomization from different atomizer surfaces in graphite-furnace atomic-absorption spectrometry

The mechanism of cobalt atomization from different atomizer surfaces in graphite-furnace atomic-absorption spectrometry has been investigated. The atomizer surfaces were pyrolytically coated graphite, uncoated electrographite, and glassy carbon. The activation energy of the rate-determining step in the atomization of cobalt (taken as the nitrate in aqueous solution) in a commercial graphite furnace has been determined from a plot of log k_s vs. 1/T (for T values greater than the appearance temperature), where k_s is a first-order rate constant for atom release, and T is the absolute temperature. The activation energy E_a, can be correlated either with the dissociation energy of CoO_(g) or with the heat of sublimation of Co_(s), formed by carbon reduction of CoO_(s), the latter being the product of the thermal decomposition of Co(NO₃)₂. The mechanism for Co atomization seems to be the same for the pyrolytically coated graphite and the uncoated electrographite surfaces, but different for the glassy carbon surface. The suggested mechanisms are consistent with the chemical reactivity of the three atomizer surfaces, and the physical and thermodynamic properties of cobalt and its chemical compounds in the temperature range involved in the charring and atomization cycle of the graphite furnace.     

Electrothermal atomic-absorption determination of vanadium

Factors such as sample nature, matrix and heating programme have been found to influence both the sensitivity and precision of the determination of vanadium by electrothermal AAS. The reciprocal sensitivity, detection limit and precision (RSD) are 55 pg, 86 pg and 4%, respectively for aqueous solutions and 88 pg, 80 pg and 4% for organic solutions. Only tungsten and nitric acid have been found to interfere appreciably. Moderately concentrated sodium chloride solutions (6%) can be analysed for vanadium (0.05 mug/ml) without background correction, as can the acid digests of phosphate rocks and crude petroleum samples.     

Determination of molybdenum by atomic-absorption spectrophotometry

A new procedure is described for precise estimation of molybdenum by atomic-absorption spectrophotometry using an airacetylene flame. Phosphoric acid was found to be effective in suppressing interference by Fe(III), Al, Sb(III), Ca, Mg, Pb and Mn(II).     

Use of complexing ligands in the determination of antimony and tin by atomic-absorption spectrometry

The atomic-absorption spectrophotometric determination of antimony is best achieved in the presence of either an ammonium fluoride, hydrochloric acid, nitric acid mixture, or one of the following complexing agents: tartaric acid, citric acid, oxalic acid, 2-mercaptopropanoic acid. The interference of the 29 metals tested is least in the ammonium fluoride-hydrochloric acid-nitric acid mixture and is similar in tartaric acid, citric acid and 2-mercaptopropanoic acid media. However, the interference is pronounced in oxalic acid. Tin can be determined if any of the complexing agents or 6M hydrochloric acid is present.     

Determination of antimony in rocks and sulphide ores by flame and electrothermal atomic-absorption spectrometry

Atomic-absorption methods for determination of antimony at mug/g levels in rocks and sulphide ores by flame atomization (FAA) and electrothermal atomization (ETAA) have been described. The FAA method involves the separation of antimony from matrix elements by extraction as the iodide into methyl isobutyl ketone containing tri-n-octylphosphine oxide, from dilute hydrochloric acid solution, followed by direct aspiration of the extract into an air-acetylene flame. If necessary, antimony is first separated from copper and lead by co-precipitation with hydrous ferric oxide from ammoniacal medium and by precipitation of lead as lead sulphate. The ETAA method involves co-precipitation of antimony with hydrous ferric oxide followed by dissolution of the precipitate in dilute nitric acid, mixing with nickel solution as releasing agent, and ETAA measurement by use of a tungsten strip atomizer.     

Determination of gold in biological materials by electrothermal atomic absorption spectrometry with a molybdenum tube atomizer

Electrothermal atomic absorption spectrometry (ETA-ASS) of gold with a molybdenum tube atomizer has been investigated. A sensitive ETA-AAS method was developed. The gold absorption signal became higher with the heating rate of the tube atomizer and as the ratio of hydrogen in the argon purge gas decreased. The optimal heating rate and the optimal gas flow rate were 5.5 C/msec and Ar 480 ml/min + H(2) 20 ml/min, respectively. The absolute characteristic mass (the mass of element giving 0.0044 abs.) of gold by the atomizer was 1.8 pg and the detection limit was 130 pg/ml (3S/N). These values were > 10 times better than those obtained with graphite atomizers, ICP and ICP-MS. The interferences caused by large amounts of interferents were evaluated. The addition of thiourea served to eliminate severe interferences. The recovery of spiked gold in biological materials was in the range of 101-106%.