Evaluation of ammonia as diluent for serum sample preparation and determination of selenium by graphite furnace atomic absorption spectrometry

A method for the determination of total selenium in serum samples by graphite furnace atomic absorption spectrometry was evaluated. The method involved direct introduction of 1:5 diluted serum samples (1% v/v NH₄OH+0.05% w/v Triton X-100^®) into transversely heated graphite tubes, and the use of 10 μg Pd+3 μg Mg(NO₃)₂ as chemical modifier. Optimization of the modifier mass and the atomization temperature was conducted by simultaneously varying such parameters and evaluating both the integrated absorbance and the peak height/peak area ratio. The latter allowed the selection of compromise conditions rendering good sensitivity and adequate analyte peak profiles. A characteristic mass of 49 pg and a detection limit (3s) of 6 μg 1⁻¹ Se, corresponding to 30 μg l⁻¹ Se in the serum sample, were obtained. The analyte addition technique was used for calibration. The accuracy was assessed by the determination of total selenium in Seronorm™ Trace Elements Serum Batch 116 (Nycomed Pharma AS). The method was applied for the determination of total selenium in ten serum samples taken from individuals with no known physical affection. The selenium concentration ranged between 79 and 147 μg l⁻¹, with a mean value of 114±22 μg l⁻¹.     

Behavior of mercury(II) salts in electrothermal atomic absorption spectrometry : Application to the Determination of Thiosulfate

Mercury(II) salts have different decomposition temperatures in a graphite tube or tantalum coil used for electrothermal atomic absorption spectrometry. The nitrate, perchlorate and acetate were spontaneously reduced to mercury vapor at room temperature, but the thiosulfate, sulfide, cyanide and bromide were reduced only on heating. Chloride and thiocyanate in a graphite furnace and iodide in a tantalum coil did not give mercury absorbance on heating. Thiosulfate (1–10 × 10^?6 M) was determined by addition to mercury(II) nitrate in acetate buffer, removing the response from the excess mercury(II) nitrate by drying below 100° C in the graphite furnace, and measuring the mercury absorbance on heating, which was proportional to the thiosulfate concentration.     

Development of a new method for direct determination of selenium associated with atmospheric particulate matter using chemical modifiers and graphite probe furnace atomic absorption spectrometry

Direct determination of selenium on or in atmospheric particulate matter (APM) has been achieved using an integrated filtration and analysis system developed in our laboratories. The filtration (sampling) and analysis system consists of a porous electrographite plate which is used initially for the purpose of collecting APM and subsequently as a probe in graphite probe furnace atomic absorption spectrometry. Selenium produced a double peak when it was atomized from such an electrographite probe. Palladium nitrate+magnesium nitrate, as a mixed chemical modifier or ascorbic acid as a chemical modifier, eliminated the double peak. The addition of the chemical modifier(s) also removed the unpredictable changes in the peak-height and the peak-area absorbance which occurred from one atomization cycle to the next if the chemical modifier was not used. Precision of 5% RSD (peak-area absorbance) was obtained for an aqueous solution of selenium standard containing 1.25 ng of selenium with palladium nitrate+magnesium nitrate mixed chemical modifier, or ascorbic acid chemical modifer. The characteristic masses and the limits of detection for the aqueous solution of selenium standard with palladium nitrate+magnesium nitrate mixed chemical modifier are 27 and 41 pg (peak-area absorbance), respectively, and with ascorbic acid chemial modifier are 29 and 36 pg, respectively (peak-area absorbance). The results of analysis of the NIST (formerly National Bureau of Standards) Standard Reference Material No. 1648, Urban Particulate Matter, for selenium with palladium nitrate+magnesium nitrate mixed chemical modifier gave a recovery of 92%, and a precision of 10% RSD, and characteristic mass and the limit of detection of 20 and 37 pg, respectively.     

Mechanism of modification by palladium in graphite furnace atomic absorption spectrometry

The effects of palladium and mixtures containing palladium on the absorbance characteristics of lead, thallium, cadmium, selenium, manganese and cobalt are described. These data, together with results of scanning electron microscopy showing the distribution of palladium on the graphite surface, indicate that palladium has a physical mechanism of analyte modification. During furnace heating, the analyte dissolves in molten palladium and may combine with it chemically. However, the rate limiting step leading to atomization appears to be diffusion of the analyte from palladium. The addition of magnesium, molybdenum or powdered carbon increases the speed of diffusion by causing palladium to form smaller droplets, and hence produces sharper absorbance peaks. Palladium becomes less effective as the atomization temperature increases, because the rate of diffusion is higher. This accounts for palladium having only a small stabilizing effect on less volatile elements such as manganese and cobalt. The addition of ascorbic acid to palladium has no significant effect on its modifying properties in a dilute nitric acid matrix. Results of kinetic studies on the atomization of gold are consistent with analyte diffusion out of palladium as the rate-limiting step leading to atomization.     

Use of transition elements to enhance sensitivity for selenium determination by graphite-furnace atomic-absorption spectrophotometry combined with solvent extraction with the APDC-MIBK system

A microanalytical method for the measurement of selenium in waters and biological materials by a flameless atomic-absorption technique has been developed. The ammonium pyrrolidinedithiocarbamate-methyl isobutyl ketone extraction system is used for separation from interfering materials such as large amounts of alkali and alkaline earth metal salts and mineral acids. The atomic-absorption sensitivity for selenium is found to be enhanced to a large extent by co-extraction of some transition metal ions. Copper(II) has been used successfully as such an additive to diminish the volatility of selenium in the graphite furnace during the ashing step of the atomization cycle. When the aqueous phase/organic solvent volume ratio is 5 and the volume injected into the graphite furnace is 20 mul, the sensitivity for selenium is 0.3 ng/ml for 1% absorption. The relative standard deviation is ca. 2%. Interference by other metal ions is prevented by masking with EDTA. The method has been applied satisfactorily for the determination of minute amounts of selenium in waters and various biological materials.     

Nickel and strontium nitrates as modifiers for the determination of selenium in wine by Zeeman electrothermal atomic absorption spectrometry

A mixed matrix modifier of nickel and strontium nitrates was used as a chemical modifier for the determination of selenium in wines by Zeeman electrothermal atomic absorption spectrometry. Wine samples were heated on a boiling water bath with small amounts of nitric acid and hydrogen peroxide. For complete elimination of interference, especially from sulfates and phosphates, selenium is complexed with ammonium pyrolidinedithiocarbamate (APDTC), extracted into methyl isobutyl ketone (MIBK), and measured by ETAAS. The graphite furnace temperature program was optimized for both aqueous and organic solutions. Pyrolysis temperatures of 1300 degrees C and 800 degrees C were chosen for aqueous and organic solutions, respectively; 2700 degrees C and 2100 degrees C were used as optimum atomization temperatures for aqueous and organic solutions, respectively. The optimum modifier mass established is markedly lower than those presented in the literature. The platform atomization ensures pretreatment stabilization up to 1100 degrees C and 1600 degrees C, respectively, for organic and aqueous selenium solutions. The procedure was verified by the method of standard addition. The investigated wine samples originated from the different regions of the Republic of Macedonia. The selenium concentration varied from not detectable to 0.93 microg L(-1).     

Matrix modification with silver for the electrothermal atomization of arsenic and selenium

Silver as a matrix modifier is shown to improve the carbon-rod atomization of both arsenic and selenium for atomic absorption spectrometry. Compared to nickel, the efficiency of silver is greater for arsenic and about the same for selenium. Silver fulfils two functions in its reaction, namely stabilization during the ashing stage and enhancement of absorbance in the final atomization.     

Nickel and strontium nitrates as modifiers for the determination of selenium in wine by Zeeman electrothermal atomic absorption spectrometry

A mixed matrix modifier of nickel and strontium nitrates was used as a chemical modifier for the determination of selenium in wines by Zeeman electrothermal atomic absorption spectrometry. Wine samples were heated on a boiling water bath with small amounts of nitric acid and hydrogen peroxide. For complete elimination of interference, especially from sulfates and phosphates, selenium is complexed with ammonium pyrolidinedithiocarbamate (APDTC), extracted into methyl isobutyl ketone (MIBK), and measured by ETAAS. The graphite furnace temperature program was optimized for both aqueous and organic solutions. Pyrolysis temperatures of 1300?°C and 800?°C were chosen for aqueous and organic solutions, respectively; 2700?°C and 2100?°C were used as optimum atomization temperatures for aqueous and organic solutions, respectively. The optimum modifier mass established is markedly lower than those presented in the literature. The platform atomization ensures pretreatment stabilization up to 1100?°C and 1600?°C, respectively, for organic and aqueous selenium solutions. The procedure was verified by the method of standard addition. The investigated wine samples originated from the different regions of the Republic of Macedonia. The selenium concentration varied from not detectable to 0.93 μg L^–1.     

Graphite furnace and flame atomic-absorption technique for thermoanalytical investigations

Aerosol particles formed from the vapour of electrothermally heated substances were introduced into an acetylene-air flame for atomization and detection. Thus individual observations could be made on condensed phase processes taking place in the furnace. Curves of absorbance vs. furnace temperature for several zinc compounds were recorded and compared with the corresponding thermoanalytical DTG-curves.     

On the uniforming of the atomization process for inorganic and organic mercury in graphite furnace atomic absorption spectrometry

The analytical performance of Pd, Au, Rh, Ir and their mixtures used as chemical modifiers has been investigated for mercury determination by graphite furnace atomic absorption spectrometry. The aim of this work was to evaluate whether chemical modification assures uniform atomization of analyte independent of its chemical form; mercury was used for this study. The investigations were performed for mercury introduced in the form of inorganic Hg(II) or organic PhHg(I). The best conditions, i.e. maximum pyrolysis temperature (450 °C), lowest temperature for atomization (1100 °C), provided almost the same sensitivity for both forms of mercury when a thermally reduced mixed modifier composed of Pd/Rh was used. The accuracy of the selected conditions was evaluated by a recovery test for various natural waters.     

Electrothermal atomization of silver in graphite furnaces. Part 2. Effects of copper,ascorbic acid and Triton X-100

The effects of copper, ascorbic acid and Triton X-100 on the atomization process of Ag are presented as a function of the initial mass of analyte and the heating rate of atomization. In general, a double pulse structure is detected, at a heating rate of 300 K s⁻¹, in the absorbance profile and its time derivative. This behavior shows up in the Arrhenius plots as two temperature regions of atomization. In the presence of Cu and Triton X-100, a low atomization energy E_a is obtained in the low temperature region and a high value of E_a, which approaches the heat of vaporization of Ag, is obtained in the high temperature region. However, in the presence of ascorbic acid, two low desorption energies are obtained in both temperature regions, suggesting a higher dispersion of particles owing to the presence of a higher number of active sites. At a heating rate of 700 K s⁻¹, a single atomization step with an atomization energy of 233 kJ mol⁻¹ and a first kinetic order of release is detected in the presence of Cu. However, in the presence of ascorbic acid and Triton X-100, two temperature regions of atomization are obtained from the Arrhenius plots, even though the absorbance profiles look continuous. In these cases, a mass dependent E_a is obtained in the low temperature region, and a low E_a with a first kinetic order of release is obtained in the high temperature region. In summary, the low value of E_a indicates vaporization from disperse particles, whereas the mass dependent, higher value of E_a indicates atomization from small clusters, the size and energy of which increase as the initial mass of Ag increases.The structure of the absorbance profiles and their time derivatives, and also the behavior of the Arrhenius plots, correlate well with those predicted by the two-precursor atomization model proposed in our previous work [1].     

Determination of selenium in water by electrothermal atomic absorption spectrometry

Summary The electrothermal atomization of selenium has been investigated for the accurate determination of selenium in water samples. Hydrogen seriously affects the atomization temperature of selenium in a molybdenum micro-tube atomizer. The atomization of selenium also suffers from serious interferences caused by salts and other elements. The extraction of selenium diethyldithiocarbamate complex serves to eliminate the interferences from the matrix. The addition of copper allows the suppression of interferences from elements extracted with selenium. The method permits the determination of selenium(IV) and selenium(VI) separately.This research was in part funded by the Ministry of Education, Science and Culture, Japan, under Grant-in-Aid for Scientific Research, for which we express our appreciation.     

Investigation of reactions involved in graphite furnace atomic absorption procedures: Part 12. A study of some factors influencing the determination of selenium

An experimental and theoretical study of various factors influencing the determination of selenium by graphite furnace atomic absorption spectrometry (g.f.a.a.s.) is reported. It is shown that the atomization efficiency can be increased as compared to the L'vov platform technique by means of a constant temperature furnace as a consequence of the possibility of choosing a higher atomization temperature. This is explained by means of high temperature equilibrium calculations, which include the formation of the thermodynamically relatively stable gaseous diselenium, hydrogen selenide and selenium sulphide. The extent of losses of selenium during thermal pretreatment was established by measurements with ⁷⁵Se for different types of selenium compounds, Se(-II)-methionine, selenite and selenate, in aqueous solutions as well as in chloride and sulphate matrices. It is shown that the addition of 20 μg of nickel is effective in stabilizing Se(IV) and Se(VI) in the presence of sodium chloride, sodium sulphate and pure water. However, in the presence of both an organic matrix (glucose) and sodium chloride, nickel is shown to lose its stabilizing effect.     

Flame-atomic absorption analysis for trace metals after electrochemical preconcentration on a wire filament

To avoid unspecific light losses in the atomic absorption analysis of trace metals in the presence of a high concentration of salts, electrochemical preconcentration on a wire filament is employed, prior to flame atomization. The elements in question are electrolyzed on to a platinum spiral filament which is then heated in an air-acetylene flame. A quartz tube is placed above the filament, to increase the sensitivity of the method. The separation technique is simple and non-destructive; a sample volume of 5–20 ml and an electrolysis time of 2–5 min are recommended. Because of the relatively low filament temperature, the method is limited to elements which are readily volatilized such as silver, bismuth, cadmium, mercury, lead, selenium, tellurium, thallium and zinc. For most elements, the detection limits are of the same order of magnitude as those of the “Delves cup” technique.     

石墨炉原子吸收法测定黑花生中的硒

该文以转基因食品黑花生为研究对象,针对硒易挥发的特点,建立了高压密闭消解-石墨炉原子吸收光谱法测定黑花生中总硒含量的测定方法.研究表明,HNO3-H2O2可使样品达到最佳消解,以Pd(NO3)2+Mg(NO3)2为基体改进剂,最佳灰化温度和原子化温度分别为500 ℃和2 000 ℃.在优化实验条件下,该方法测定硒的线性...     

Effects of various salts on the determination of arsenic by graphite furnace atomic absorption spectrometry. Direct determination in seawater

The effect of Na, Mg, Ca and Sr as their nitrate, chloride and sulfate salts and seasalt, with and without the use of palladium, on the determination of arsenic by electrothermal atomic absorption spectrometry was investigated. In the absence of any stabilizing agent, arsenic was partially lost as molecular species at low temperatures. The effect of salts on the shape of the atomization signal, the integrated absorbance and the stabilizing effect were highly dependent both on their nature and mass. By trapping arsenic, oxide species resulting from the decomposition of nitrate salts induced a high stabilization effect depending on their vaporization temperatures: MgO approximately CaO>SrO>Na2O. The stabilization effect of chlorides occurred about 200 degrees C lower and depended on mass, volatility and hydrolytic properties: SrCl2>CaCl2>MgCl2 approximately NaCl. The effect of sulfates was mainly dependent on their decomposition/vaporization mechanisms, and in the presence of Na2SO4 or CaSO4 a strong chemical interference effect was observed. Palladium stabilized arsenic in the presence of nitrates, chlorides or even sulfates, leading to a similar delaying effect, signal shape and integrated absorbance. Seasalt induced also important modifications to the atomization signal of As. Moreover, an interference effect was observed, which could probably be attributed to the simultaneous vaporization of sulfate in seasalt. In seawater, Pd suppressed this interference effect and permitted to use a high pyrolysis temperature up to 1400 C to remove the major part of the seawater matrix before atomization. Under optimized conditions, the detection limit for As obtained in unmodified seawater in the presence of Pd was 0.34 microg L(-1) for a 10 microl sample.     

Determination of mercury in environmental samples by cold vapour generation and atomic-absorption spectrometry with a gold-coated graphite furnace

Mercury is determined at below the pg/ml level by a combination of cold vapour generation, trapping in a gold-coated graphite furnace and atomic-absorption detection. The mercury is reduced to the element by stannous chloride, stripped from solution by a stream of nitrogen and collected on a gold-coated porous graphite disk in a graphite furnace. It is then atomized by increasing the graphite furnace temperature and detected by an atomic-absorption spectrophotometer. The absolute detection limit and the characteristic mass were found to be 5 and 20 pg for 0.0044 absorbance, respectively. The concentration limit of detection was 0.1 pg/ml for a 50-ml sample, and the linear dynamic range covered three orders of magnitude. The precisions of the measurements were 2.7% for 0.1 ng and 2.6% for 2 ng of mercury. Analyses of NBS and NIES reference materials showed quantitative recovery. Analytical results obtained by the technique are presented for natural waters, marine biota and sediments.     

Effects of interfering elements and chemical modifier on the activation energy of electrothermal atomization of selenium

In order to obtain additional insight into the mechanism of stabilization of selenium by palladium modification and to investigate the interference mechanism of Na, K, Mg and Ca on selenium atomization, the appearance temperature and the activation energy of atomization of selenium with or without the presence of the modifier and with or without the presence of the concomitant element, have been evaluated and discussed.     

Determination of 1 ng/l. Levels of mercury in water by electrothermal atomization atomic-absorption spectrometry after solvent extraction

Optimization of the furnace parameters for electrothermal atomization of mercury leads to a characteristic mass of 20 pg in aqueous solution and 30 pg in chloroform extracts (with Zeeman correction). With a single-step solvent extraction from 100 ml of sample, performed in the sampling vessel, and direct injection of 400 μl of the extract into the furnace, a characteristic concentration of 0.8 ng/l. is reached.