Solid Sampling Electrothermal Atomic Absorption Research Articles

Rapid and sensitive determination of trace Cd in carbonate samples using direct solid sampling electrothermal vaporization atomic absorption spectrometry

The accurate determination of cadmium (Cd) hosted and accumulated in sedimentary carbonate remains challenging due to its low concentration (ng·g−1) and complex matrix. Conventional methods, such as inductively coupled plasma mass spectrometry (ICP-MS) and graphite furnace atomic absorption spectrometry (GF-AAS), which typically rely on liquid sampling and sample digestion, are tedious, labor-intensive and time-consuming. In this study, a rapid and sensitive method for the direct determination of carbonate-hosted Cd was developed based on solid sampling electrothermal atomic absorption spectrometry (SS-ETV-AAS). This method eliminates the need of acid digestion procedure, allowing the entire analysis, including sample preparation, to be completed within 10 min. To minimize the carbonate matrix effect, ethylene diamine tetra acetic acid disodium salt (EDTA-2Na) was proposed as matrix modifier to facilitate the release of Cd, enabling fast and accurate determination of trace Cd in carbonate samples. Under optimized conditions, the Cd detection limits was found to be as low as 0.17 ng·g−1, and repeatability (relative standard deviation, RSD) was better than 8 % (n = 7). The accuracy of the proposed SS-ETV-AAS was verified by analyzing five carbonate certified reference materials (GBW07127, GBW07129, GBW07130, GBW07135 and JDo-1), two soil certified reference materials (GBW07404a, GBW07405), as well as several actual carbonate samples. All these results demonstrate that the proposed SS-ETV-AAS method provides a simple, rapid and sensitive approach for measuring trace Cd in carbonates.

Fast Detection of Cadmium in Chocolate by Solid Sampling Electrothermal Vaporization Atomic Absorption Spectrometry and Its Application on Dietary Exposure Risk Assessment.

In this work, a rapid detection method using solid sampling electrothermal vaporization atomic absorption spectrometry (SS-ETV-AAS) was established for cadmium in chocolate. The instrumental system includes a solid sampling ETV unit, a catalytic pyrolysis furnace, an AAS detector, and a gas supply system with only an air pump and a hydrogen generator. Herein, MgO material with 1.0–1.5 mm particle size was first employed to replace the kaolin filler previously used to further shorten the peak width and to thereby improve the sensitivity. With 350 mL/min of air, a chocolate sample was heated for 25 s from 435 to 464 °C to remove water and organic matrices; then, after supplying 240 mL/min hydrogen and turning down air to 120 mL/min, a N2/H2 mixture gas was formed to accelerate Cd vaporization from chocolate residue under 465 to 765 °C. Under the optimized conditions, the detection limit (LOD) was obviously lowered to 70 pg/g (vs. previous 150 pg/g) with R2 > 0.999; the relative standard deviations (RSD) of repeated measurements for real chocolate samples ranged from 1.5% to 6.4%, indicating a favorable precision; and the Cd recoveries were in the range of 93–107%, proving a satisfied accuracy. Thus, the total analysis time is less than 3 min without the sample digestion process. Thereafter, 78 chocolate samples with different brands from 9 producing countries in China market were collected and measured by this proposed method. Based on the measured Cd concentrations, a dietary exposure assessment was performed for Chinese residents, and the target hazard quotient (THQ) values are all less than 1, proving no significant health risk from intaking chocolate cadmium for Chinese residents.

Novel solid sampling electrothermal vaporization atomic absorption spectrometry for fast detection of cadmium in grain samples

In this work, a novel and green solid sampling method of Cd in grain samples was established based on electrothermal vaporization atomic absorption spectrometry (ETV-AAS).

Direct solid sampling electrothermal atomic absorption spectrometric determination of toxic and potentially toxic elements in certified reference materials of brown coal fly ash

This work describes a method for the direct determination of Bi, Cd, Cr, Ni, Pb, Sb, Sn and Zn in reference materials of brown coal fly ash, using solid sampling electrothermal atomic absorption spectrometry. The use of chemical modifiers was found to be necessary for obtaining reproducible and sufficiently sensitive signals for the analytes under study. The mixture of Pd and Mg(NO3)2 was used for the determination of Bi, Cd, Pb, Sb, Sn and Zn, W (permanent modifier) in combination with Mg(NO3)2 (as aqueous modifier) provided well-defined signal profiles for Cr and Ni determination in coal fly ash samples. A systematic study focused on the use of alternative (less sensitive) lines for obtaining sufficient sensitivity. The following analytical lines were used: Bi 306.8nm, Cd 326.1nm, Cr 520.6nm, Ni 305.1nm, Pb 205.3nm, Sb 206.8nm, Sn 300.9nm, Zn 307.6nm. The limits of detection were 0.057μg g−1 for Bi, 0.21μg g−1 for Cd, 1.1μg g−1 for Cr, 1.4μg g−1 for Ni, 4.0μg g−1 for Pb, 0.13μg g−1 for Sb, 0.33μg g−1 for Sn and 16μg g−1 for Zn, respectively.

Stabilizing Agents for Calibration in the Determination of Mercury Using Solid Sampling Electrothermal Atomic Absorption Spectrometry

Tetramethylene dithiocarbamate (TMDTC), diethyldithiocarbamate (DEDTC), and thiourea were investigated as stabilizing agents for calibration purposes in the determination of mercury using solid sampling electrothermal atomic absorption spectrometry (SS-ETAAS). These agents were used for complexation of mercury in calibration solutions and its thermal stabilization in a solid sampling platform. The calibration solutions had the form of methyl isobutyl ketone (MIBK) extracts or MIBK-methanol solutions with the TMDTC and DEDTC chelates and aqueous solutions with thiourea complexes. The best results were obtained for MIBK-methanol solutions in the presence of 2.5 g L−1 TMDTC. The surface of graphite platforms for solid sampling was modified with palladium or rhenium by using electrodeposition from a drop of solutions. The Re modifier is preferable due to a higher lifetime of platform coating. A new SS-ETAAS procedure using the direct sampling of solid samples into a platform with an Re modified graphite surface and the calibration against MIBK-methanol solutions in the presence of TMDTC is proposed for the determination of mercury content in solid environmental samples, such as soil and plants.

Determination of impurities for controllable growth of high quality optical fluorite

AbstractNatural fluorite is used for growing CaF2 boules from melt by an improved technique. Chemical treatment of the starting ore decomposes the accessory minerals, thus producing small amounts of the oxides of Si, Al, and Fe insoluble in the melt, whereas the overall content of rare earth elements (REEs) of hundreds of μg g−1, remains unchanged. Analytical techniques and optical measurements provide for assessing the concentration range and trends in the distribution of residual metal impurities along the height of the boules. Solid sampling electrothermal atomic absorption spectrometry (SS-ETAAS) gives good reproducibility for impurities’ distribution within a large concentration range of 0.1–10 μg g−1. The concentrations of Zn and Cu determined were found to vary within the lowest tenths of μg g−1 range in the starting portions of chemically treated fluorspar and a batch of boules produced subsequently. The concentrations of both elements show a decreasing trend towards the top section within the confidential interval, the width of which confirms the definite in homogeneities in their distribution at those concentration levels. The Fe occurs in the boules below the detection limit, while the content of lead diminishes rapidly towards their upper section, probably due to a shorter path in the liquid phase before any vapour phase transition proceeds. A satisfactory correlation is found between the Pb concentration in ng g−1-range and light-absorption peak intensity at 204 nm, the precise determination of which is impeded due to the overlapping bands and the light-scattering effect. Reliable determination of impurities enables optimisation of the basic purification — growing stages for the production of high grade crystals.

Determination of metal impurities in carbon nanotubes by direct solid sampling electrothermal atomic absorption spectrometry

Metal impurities (Al, Cd, Co, Cr, Cu, Mg, Mn and Pb) were determined in carbon nanotubes (CNTs) by direct solid sampling electrothermal atomic absorption spectrometry (DSS-ET AAS, deuterium lamp background corrector). Parameters as pyrolysis and atomization temperatures, use of Pd as chemical modifier, feasibility of calibration using aqueous standard solutions and maximum sample mass were investigated. Results obtained by the proposed method were compared with those obtained by neutron activation analysis (NAA) and also by inductively coupled plasma mass spectrometry (ICP-MS) and inductively coupled plasma optical emission spectrometry (ICP OES) after high-pressure microwave assisted wet digestion and microwave-induced combustion methods. No significant differences were observed between the results obtained by DSS-ET AAS, ICP-MS and ICP OES after both digestion methods and also by NAA. Calibration was performed using aqueous standards. Background signals were always lower than 0.02 (peak height) and no chemical modifier was used. The proposed method allowed the determination of all elements in CNTs with lower limits of detection in comparison with other techniques.

A rapid method for the determination of Pb, Cu and Sn in dried tomato sauces with solid sampling electrothermal atomic absorption spectrometry

In this work, lead, copper and tin were determined in tomato sauces by solid sampling graphite furnace atomic absorption spectrometry (SS-GFAAS) and the results were compared with those obtained after sample digestion. The tomato sauce samples were dried at 90°C for 12h and directly introduced into the graphite furnace by means of solid auto sampler. Alternatively the dried samples were digested with concentrated HNO3 (65%) and pipetted into the graphite furnace. After the optimization of the experimental parameters, the average lead, copper and tin concentrations found by the solid sampling and digestion methods in 10 different kinds of tomato sauce samples were not significantly different at 95% confidence level. For solid sampling technique, the limits of detection (LOD) for Cu, Sn and Pb were 10.4, 3.2 and 0.4ng/g, respectively. Whereas for digestion method, for Cu, Sn and Pb were 6.7, 2.7 and 0.3ng/g, respectively. The proposed solid sampling technique was fast, simple, the risks of contamination and analyte loss were low.

A rapid solid sampling method for determination of nickel and copper along human hair by ETAAS

A procedure for copper and nickel determination in scalp hair by solid sampling electrothermal atomic absorption spectrometric method was described. The hair samples (0.02 to 0.4 mg) were inserted directly on the platforms of solid sampling autosampler. The effects of pyrolysis temperature, atomization temperature, the amount of sample as well as addition of a modifier (Pd/Mg) and/or auxiliary digesting agents (hydrogen peroxide and nitric acid) and/or a surfactant (Triton X-100) on the determination of copper and nickel by solid sampling atomic absorption spectrometry were investigated. After optimization of parameters, the average recoveries of copper in two different certified reference hair samples were 105.7 and 97.6%. The recoveries of nickel in the both certified reference hair samples were in 95.2 and 96.4%. The limits of detection (3σ, N = 10) for copper and nickel were 22 ng/g and 35 ng/g, respectively. Heterogenous distribution of analyte in microscale for segmental analysis could be determined which is important to know that analyte quantity and time of poisoning of a person was exposed. For this purpose, 0.5 cm of pieces were cut along one or a few close strands and analyzed by solid sampling. This process could not be performed by wet-digestion method because 50 mg of sample is needed each time. Finally, the method was applied for the determination of copper and nickel concentrations in the hairs of different persons.

A study of the direct determination of Cd, Cr, Cu, Pb and Zn in certified reference materials of soils by solid sampling electrothermal atomic absorption spectrometry

A simple and rapid method for the direct determination of Cd, Cr, Cu, Pb and Zn in soil was developed. The method was developed using three certified reference materials of soil: Eutric Cambisol, Orthic Luvisols and Rendzina, which differed in their matrix composition. Chemical modifiers were essential to achieve reproducible and interference-free signals for the analytes studied. The best results were obtained with a Pd/Mg(NO 3) 2 admixture for the determination of Cd, Pb and Zn and NH 4F for Cu. The combination of W (as a permanent modifier) and Mg(NO 3) 2 provided well-defined signal profiles for Cr. The following spectral lines were used: Cd 228.8 nm, Cr 520.6 nm, Cu 218.2 nm, Pb 205.3 nm and Zn 307.6 nm. The limit of detection was 4.2 ng g − 1 for Cd, 1.1 μg g − 1 for Cr, 0.5 μg g − 1 for Cu, 1.3 μg g − 1 for Pb and 8.6 μg g − 1 for Zn for the maximum sample mass used. Under optimized conditions, the analyte and matrix were separated effectively in situ, and aqueous standards could be used for calibration.

Electrochemical Modification of a Graphite Platform for a Solid Sampling Electrothermal Atomic Absorption Spectrometry of Mercury

An electrodeposited palladium and iridium/gold mixture has been investigated as a chemical modifier for mercury determination in environmental samples by solid sampling electrothermal atomic absorption spectrometry. Electrochemical procedures of platform surface modification performed in a cell with 20 ml of solution, and in a drop of modifier solution have been optimized. Simple electrolysis in a drop was found to be the most consistent, taking the reproducibility as the major criterion. A total mass of 250 µg of electrodeposited palladium or an iridium/gold mixture was used. The lifetime of 60 - 70 firings for a deposited iridium/gold mixture was smaller than that for palladium with a lifetime of 100 - 120 firings. The detection limit was 120 pg Hg. Different sample masses of between 0.1 and 10 mg were weighed into modified platforms according to the mercury content. The results obtained for mercury in environmental samples as soils, sediments and plant, using solid sampling and calibration against aqueous standards stabilized by potassium permanganate, were in good agreement with those achieved by using the thermal deposition of modifiers and with measurements by pyrolysis atomic absorption spectrometry with gold amalgamation.

A practical solid sampling method for the determination of lead in chewing gum by electrothermal atomic absorption spectrometry

In this study, the lead concentrations of chewing gum samples having different compositions were determined by solid sampling electrothermal atomic absorption spectrometry. In order to optimise the experimental conditions, the effects of pyrolysis temperature, atomization temperature, sample amount and sample thermal pre-treatment, on the analyte sensitivity were investigated. The samples were ashed at 400 °C for 2 h prior to directly determined by SS-ETAAS applying 600 °C of pyrolysis and 1600 °C of atomization temperatures without to add a modifier, acid and/or surfactant. The relationship between sample mass and integrated absorbance was linear up to 1.2 mg of sample; for higher sample mass the relationship was no longer linear, irrespective of the lead content. In addition, the thermally treated chewing gum samples were digested using concentrated HNO 3. The lead concentrations found by the two methods in 27 different kinds of samples were not significantly different at 95% confidence level. The proposed solid sampling technique was fast, simple, the risks of contamination and analyte loss were low. Detection limit (3 σ) for lead was 0.017 ng/g.

Utilization of W/Mg(NO 3) 2 modifiers for the direct determination of As and Sb in soils, sewage sludge and sediments by solid sampling electrothermal atomic absorption spectrometry

A simple method has been developed for the determination of arsenic and antimony in environmental samples by solid sampling electrothermal atomic absorption spectrometry, which was validated using certified reference materials of soils (S-VM — Soil Eutric Cambisol; S-MS — Soil Orthic Luvisols; S-SP — Soil Rendzina), sewage sludge (WT-L; WT-M) and sediments (NIES2; GBW07906). The analytical procedure combines solid sampling with utilization of a matrix modifier admixture containing 5 µg of W and 5 µg of Mg. The tungsten in the admixture serves to stabilize the solid matrix during atomisation, which results in dramatically reduced non-specific absorption compared with the conventional palladium modifier. Magnesium was efficient in reducing the accumulation of the matrix residue on the platform. An alternative resonance line of 197.2 nm for arsenic and 206.8 nm for Sb was used in order to eliminate the spectral interferences caused by aluminum compounds, and silicon and iron compounds, respectively. Under optimized experimental conditions, the effective in situ analyte/matrix separation was achieved so that the use of aqueous standards for calibration became possible. With the modifier, a 3 SD detection limit of 0.5 µg g − 1 As and 0.1 µg g − 1 Sb and 10 SD quantification limit of 1.7 µg g − 1As and 0.3 µg g − 1 Sb and a characteristic mass of 65 pg As and 53 pg Sb were obtained. For all the matrices under scrutiny, a good agreement with certified values was achieved with RSD values less than 10%.

Determination of lead in hair and its segmental analysis by solid sampling electrothermal atomic absorption spectrometry

A rapid and practical solid sampling electrothermal atomic absorption spectrometric method was described for the determination of lead in scalp hair. Hair samples were washed once with acetone; thrice with distilled-deionized water and again once with acetone and dried at 75 °C. Typically 0.05 to 1.0 mg of dried samples were inserted on the platforms of solid sampling autosampler. The effects of pyrolysis temperature, atomization temperature, the amount of sample as well as addition of a modifier (Pd/Mg) and/or auxiliary digesting agents (hydrogen peroxide and nitric acid) and/or a surfactant (Triton X-100) on the recovery of lead were investigated. Hair samples were washed once with acetone; thrice with distilled-deionized water and again once with acetone and dried at 75 °C. Typically 0.05 to 1.0 mg of dried samples were inserted on the platforms of solid sampling autosampler. The limit of detection for lead (3 σ, N = 10) was 0.3 ng/g The addition of modifier, acids, oxidant and surfactant hardly improved the results. Due to the risk of contamination and relatively high blank values, the lead in hair were determined directly without adding any reagent(s). Finally, the method was applied for the segmental determination of lead concentrations in hair of different persons which is important to know when and how much a person was exposed to the analyte. For this purpose, 0.5 cm of pieces were cut along the one or a few close strands and analyzed by solid sampling.

Arsenic determination in pharmaceutical grade barium sulfate using direct solid sampling electrothermal atomic absorption spectrometry

A method for arsenic determination in pharmaceutical grade BaSO4 by solid sampling electrothermal atomic absorption spectrometry (SoS-ET AAS) is described. Two background (BG) correction systems, deuterium and Zeeman-effect (Z), were evaluated. Background was decreased by using hydrogen combined with Pd. Accurate and precise results were obtained using Z-SoS-ET AAS. Relative standard deviation using Z-SoS-ET AAS was lower than 9.5%. Limit of detection was 0.005 μg g-1 and characteristic mass was 25.4 pg. Results were also compared with those obtained using the preparation method suggested by European Pharmacopoeia for BaSO4 followed by determination using inductively coupled plasma optical emission spectrometry and inductively coupled plasma mass spectrometry. Results were around 20% lower than results obtained using the proposed method. Some advantages as simplicity, higher sample throughput were found when compared with the official method currently described in pharmacopoeia.

Comparison of atomic absorption, mass and X-ray spectrometry techniques using dissolution-based and solid sampling methods for the determination of silver in polymeric samples

In this work, the capabilities and limitations of solid sampling techniques – laser ablation inductively coupled plasma mass spectrometry (LA-ICPMS), wavelength dispersive X-ray fluorescence spectrometry (WD-XRFS) and solid sampling electrothermal atomic absorption spectrometry (SS-ETAAS) – for the determination of silver in polymers have been evaluated and compared to those of acid digestion and subsequent Ag determination using pneumatic nebulization ICPMS (PN-ICPMS) or flame AAS (FAAS). In a first stage, two dissolution procedures were examined: conventional acid digestion in a Kjeldahl flask and the combination of dry ashing and microwave-assisted digestion. Accurate results for Ag could be obtained, although occasionally, problems of analyte losses and/or incomplete dissolution were observed. LA-ICPMS shows potential for direct analysis of solid materials, but calibration was found to be difficult. A polypropylene sample was used as standard. This approach provided satisfactory results for other polypropylene samples and even for other types of plastics, provided that the 13C + signal was used as internal reference, correcting for variations in ablation efficiency. However, the results for polyoxymethylene were overestimated. Similar calibration problems appeared with WD-XRFS, due to differences in absorption efficiency of X-rays. In this case, the accuracy could be improved by using a matrix correction procedure, which however required the matrix composition to be known into sufficient detail. SS-ETAAS, proved to be a fast approach that allowed accurate determination of Ag in polymers using aqueous standard solutions for calibration. Due to the high Ag content and the excellent sensitivity, the use of a 3-field mode Zeeman-effect background correction system was essential for the extension of the working range.

Chromium determination in pharmaceutical grade barium sulfate by solid sampling electrothermal atomic absorption spectrometry with Zeeman-effect background correction

A procedure for chromium (Cr) determination in pharmaceutical grade barium sulfate by direct solid sampling electrothermal atomic absorption spectrometry (DSS-ET AAS) with Zeeman-effect background correction was developed. Operational conditions for the proposed procedure and the use of citric acid, ammonium phosphate, palladium and magnesium nitrate as chemical modifiers were evaluated. Pyrolysis and atomization temperatures were set at 1500 and 2400 °C, respectively and the use of matrix modifiers did not improve these conditions. Graphite platform presented high degradation rate, but minima changes were observed in the sensitivity or signal profile. Samples (0.3–1 mg) were weighted and introduced into the furnace using a manual solid sampling system. The linear concentration range of the calibration curve was from 100 to 1800 pg ( R 2 > 0.995). The characteristic mass was 7.7 pg and the limit of detection was 2.4 pg. Chromium concentration in commercial samples ranged from 0.45 to 1.06 μg g −1 and these results were confirmed by standard addition method. The mean reproducibility was 12% ( n = 20 in a 3-day period) and repeatability was less than 9%. Results obtained using inductively coupled plasma optical emission spectrometry and conventional electrothermal atomic absorption spectrometry after extraction with HNO 3 were around 20% lower than those obtained by the proposed procedure. It was assumed that the low results were due to incomplete extraction even using hard conditions related to temperature and pressure. The proposed procedure by DSS-ET AAS provided some advantages related to recommended pharmacopoeias methodology, as lower risks of contamination and analyte losses, higher specificity, accuracy and sensitivity, no toxic or unstable reagents are required, and calibration with aqueous standards was feasible.

Method development for the determination of manganese, cobalt and copper in green coffee comparing direct solid sampling electrothermal atomic absorption spectrometry and inductively coupled plasma optical emission spectrometry

A method has been developed for the determination of cobalt, copper and manganese in green coffee using direct solid sampling electrothermal atomic absorption spectrometry (SS-ET AAS). The motivation for the study was that only a few elements might be suitable to determine the origin of green coffee so that the multi-element techniques usually applied for this purpose might not be necessary. The three elements have been chosen as test elements as they were found to be significant in previous investigations. A number of botanical certified reference materials (CRM) and pre-analyzed samples of green coffee have been used for method validation, and inductively coupled plasma optical emission spectrometry (ICP OES) after microwave-assisted acid digestion of the samples as reference method. Calibration against aqueous standards could be used for the determination of Mn and Co by SS-ET AAS, but calibration against solid CRM was necessary for the determination of Cu. No significant difference was found between the results obtained with the proposed method and certified or independently determined values. The limits of detection for Mn, Cu and Co were 0.012, 0.006 and 0.004 μg g −1 using SS-ET AAS and 0.015, 0.13 and 0.10 μg g −1 using ICP OES. Seven samples of Brazilian green coffee have been analyzed, and there was no significant difference between the values obtained with SS-ET AAS and ICP OES for Mn and Cu. ICP OES could not be used as a reference method for Co, as essentially all values were below the limit of quantification of this technique.

A direct solid sampling electrothermal atomic absorption spectrometry method for the determination of silicon in biological materials

A solid sampling electrothermal atomic absorption spectrometry method for direct determination of trace silicon in biological materials was developed and applied to analysis of pork liver, bovine liver SRM 1577b and pure cellulose. The organic matrix was destroyed and expelled from the furnace in the pyrolysis stage involving a step-wise increasing the temperature from 160 °C to 1200 °C. The mixed Pd/Mg(NO 3) 2 modifier has proved to be the optimum one with respect to the achievement of maximum sensitivity, elimination of the effect of the remaining inorganic substances and the possibility of using calibration curves measured with aqueous standard solutions for quantification. For the maximum applicable sample amount of 6 mg, the limit of detection was found to be 30 ng g − 1 . The results were compared with those obtained by different spectrometric methods involving sample digestion, by electrothermal atomic absorption spectrometry using slurry sampling, by wavelength dispersive X-ray fluorescence spectrometry and by radiochemical neutron activation analysis. The method seems to be a promising one for analysis of biological materials containing no significant fraction of silicon in form of not naturally occurring volatile organosilicon compounds. The still incessant serious limitations and uncertainties in the determination of trace silicon in solid biological materials are discussed.

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 TiO 2–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 (3 σ 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.