The application of solid sorbents for the purification of aluminum contaminated chemicals used as modifiers in electrothermal atomic absorption spectrometry

Various microcolumns with solid sorbents (ion exchange resins, functionalised cellulose sorbents, chelating resins) have been tested with respect to their ability for the purification of aluminum contaminated chemicals used as modifiers in electrothermal atomic absorption spectrometry. The purification of NaNO₃, Mg(NO₃)₂, K₂SO₄ and (NH₄)₂HPO₄ has been the most effective with an almost 100% efficiency, when Spheron-Oxine was used as chelating resin. The sorption of aluminum from KOH solution has been found to be very high (around 90%) for all investigated sorbents. However, the best results have been obtained with anion-exchange resins. It has been difficult to purify concentrated mineral acids (HCl, H₂SO₄). A retention of aluminum above 80% has been achieved only when Cellex P, Chelex 100 or Amberlite XAD-2 have been used.     

Determination of vanadium in mussels by electrothermal atomic absorption spectrometry without chemical modifiers

A method was developed for the quantitative determination of total vanadium concentration in mussels via electrothermal atomic absorption spectrometry (ETAAS). After the microwave digestion of the samples, a program using temperatures of 1600 °C and 2600 °C for ashing and atomization respectively, without any matrix modifiers, allowed us to obtain results that were satisfactory since they agreed closely with certified reference material values. The detection limit was 0.03 mg kg^–1 (dry weight), indicating that the method is suitable for the analysis of mussel samples. This determination was compared with matrix modifiers that have been reported previously. The method was applied to various cultivated and wild mussels from the Galician coast, yielding levels below 1 mg kg^–1 (wet weight).     

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).     

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.     

A solid solution theory for matrix modification in electrothermal atomic absorption spectrometry

The kinetics of evaporation of the volatile analytes Pb and Cd in the presence of Ce(IV) introduced as the chemical modifier (NH₄)₂Ce(NO₃)₆ have been studied. The experimental results obtained are found to be in acceptable agreement with the regular solution model applied as a theoretical approach. Comparison with the results from previous investigation on the Pb/W analyte-modifier couple is made. An attempt is also made to explain some effects connected with the application of modifiers as described in the literature within the framework of the present model.     

Chemical modifiers in the determination of molybdenum in human serum by electrothermal atomic absorption spectrometry

Summary Various modifiers were investigated for the molybdenum determination in human serum samples by electrothermal atomization atomic absorption spectrometry. Methods with magnesium nitrate, barium difluoride, nitric acid, palladium-magnesium nitrate and palladium-hydroxylamine were studied by introducing the serum samples directly into the graphite furnace with 0.2% triton X-100. The mineralisation and atomization curves, the amount of modifier and the calibration and addition graphs were studied in all instances. The characteristic masses were 18, 22, 17, 12 and 13 pg of molybdenum for magnesium nitrate, barium difluoride, nitric acid, palladium-magnesium nitrate and palladium-hydroxylamine, respectively. The precision, accuracy and interferences of the methods were also investigated.     

Determination of silicon using electrothermal Zeeman atomic absorption spectrometry in presence of some transition metals as modifiers

The transition metals ions Cr(III), Mn(II), Fe(III), Co(II), Ni(II), and Zn(II) in addition to Ca(II) have been used as modifiers in the determination of silicon using electrothermal Zeeman atomic absorption spectrometry. Co(II) proved to be the best. Graphite tubes treated with zirconium, in the presence of Co(II) as a modifier, exhibit higher sensitivity by a factor of five than untreated tubes. The modifier concentration and ashing and atomization temperatures have been optimized. Also interference of different inorganic cations and anions was studied.     

The tube-in-tube technique in electrothermal atomic absorption spectrometry

Summary A new tube-in-tube is presented. It consists of a small graphite tube which is inserted into a usual Perkin-Elmer graphite oven. Three bars, 1×1 mm over the whole length of the tube, prevent direct contact with the outer one and smoothe the temperature profile within the tube. It causes a thermal delay in the atomization of the atomic cloud. Thus, expulsion of the atomic cloud by the thermally expanding inert gas grows less important compared to its growth. A significant increase of sensitivity is the result.

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Die Rohr-in-Rohr-Technik bei der elektrothermalen Atomabsorptions-SpektrometrieII. Das Dreisteg-Rohr

Zusammenfassung Ein neuer Rohr-in-Rohr-Atomisator wird vorgestellt. Er besteht aus einem kleinen Graphitrohr, welches in ein übliches Perkin-Elmer-Graphitrohr hineingebracht wird. Drei Stege (1×1 mm) über die gesamte Rohrlänge verhindern den direkten Kontakt mit dem Außenrohr und glätten das Temperaturprofil im Innenrohr. Die Atomisierung erfolgt thermisch verzögert. Deshalb verliert das Austreiben der Atomwolke durch das sich thermisch ausdehnende Intergas im Verhältnis zu deren Anwachsen an Bedeutung. Ein deutlicher Anstieg der Meßempfindlichkeit ist das Ergebnis.

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Herrn Prof. Dr. W. Fresenius zum 70. Geburtstag gewidmet

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Part I: Atomspektrometrische Spurenanalytik, Bd. 2 (B. Welz, Ed.). Verlag Chemie Weinheim — in print     

Fluoride matrix modifiers for the determination of aluminum by graphite furnace atomic absorption spectrometry

A method was tested for the determination of aluminum by graphite furnance atomic absorption spectrometry using hydrofluoric acid and cesium fluoride as matrix modifiers. Alunimum trifluoride is stable to 1291°C, after which it sublimes to form AlF₃ gas. The subsequent gas-phase atomization of AlF₃ occurs rapidly, and produces clean, sharp absorption peaks. This method has a detection limit of 7 pg Al at a confidence interval of 95%. The method is fairly insensitive to interferences, with the exception of strongly complexing organic acids. The addition of CuF₂ to the matrix appears to eliminate interference from organic acids, but was found to produce a high background absorbance and to shorten the life of the graphite tube.     

Direct solid sampling electrothermal atomic absorption spectrometry for the analysis of high-purity niobium pentaoxide

A direct solid sampling electrothermal atomic absorption spectrometry (SoS-ETAAS) method for ultratrace analysis of powdered niobium pentaoxide for Al, Co, Cr, Cu, Fe, K, Mg, Mn, Na, Ni and Zn has been developed. The elements K, Mg, Na and Zn could be determined without any chemical modification. However, in the determination of the elements Al, Co, Cr, Cu, Fe, Mn and Ni, serious matrix-caused non-spectral interferences and background occurred which made their determination impossible. This problem was remedied by conversion of the niobium pentaoxide matrix into the thermally stable niobium carbide by using methane atmosphere during the pyrolysis stage. The development resulted in establishing an extraordinary powerful method for the analysis of niobium pentaoxide in term of limits of detection, accuracy, simplicity and analysis time. Quantification was performed using calibration curves measured with aqueous standard solutions. The accuracy was checked by comparing the results with those obtained by ETAAS in analysis of slurries and digests of the sample. Due to almost complete freedom of blank and high applicable sample amounts (up to 15 mg), extremely low limits of detection (0.5–2 ng/g) were achieved.     

Direct solid sampling electrothermal atomic absorption spectrometry for the analysis of high-purity niobium pentaoxide

A direct solid sampling electrothermal atomic absorption spectrometry (SoS-ETAAS) method for ultratrace analysis of powdered niobium pentaoxide for Al, Co, Cr, Cu, Fe, K, Mg, Mn, Na, Ni and Zn has been developed. The elements K, Mg, Na and Zn could be determined without any chemical modification. However, in the determination of the elements Al, Co, Cr, Cu, Fe, Mn and Ni, serious matrix-caused non-spectral interferences and background occurred which made their determination impossible. This problem was remedied by conversion of the niobium pentaoxide matrix into the thermally stable niobium carbide by using methane atmosphere during the pyrolysis stage. The development resulted in establishing an extraordinary powerful method for the analysis of niobium pentaoxide in term of limits of detection, accuracy, simplicity and analysis time. Quantification was performed using calibration curves measured with aqueous standard solutions. The accuracy was checked by comparing the results with those obtained by ETAAS in analysis of slurries and digests of the sample. Due to almost complete freedom of blank and high applicable sample amounts (up to 15 mg), extremely low limits of detection (0.5-2 ng/g) were achieved.     

Chemical modifiers in arsenic determination in biological materials by tungsten coil electrothermal atomic absorption spectrometry

Palladium, iridium, and rhodium are evaluated as possible chemical modifiers in the determination of As in digest solutions of biological materials (human hair and clam) by tungsten coil electrothermal atomic absorption spectrophotometry (TCA-AAS). The modifier in solution was applied onto the coil and thermally pre-reduced; the pre-reduction conditions, the amount of modifier, and the thermal program were optimized. Palladium was not satisfactory, whereas Ir and Rh were effective modifiers and rendered better relative sensitivity for As by a factor of 1.4 and 1.9, respectively compared to the case without modifier. Upon optimization of thermal conditions for As in pre-reduced Ir (2.0 µg) and Rh (2.0 µg) modifiers and in the digest solutions of the study matrices, Rh (2.0 µg) was more effective modifier and was selected as such. The mean within-day repeatability was 2.8% in consecutive measurements (25–100 µg L^–1) (3 cycles, each of n=6) and confirmed good short-term stability of the absorbance measurements. The mean reproducibility was 4.4% (n=20 in a 3-day period) and the detection limit (3 _blank/slope) was 29 pg (n=15). The useful coil lifetime in Rh modifier was extended to 300–400 firings. Validation was by determination of As in the certified reference material (CRM) of Oyster tissue solution with a percentage relative error (E _rel%) of 2% and percentage relative standard deviation (RSD%) of 3% (n=4), and by analytical recovery of As spiked in CRM of human hair [94±8% (n=4)]. The methodology is simple, fast (sample readout frequency 21 h^–1), reliable, of low cost, and was applied to the determination of As in hair samples of exposed and unexposed workers.     

Determination of lead in aluminum and magnesium antacids using electrothermal atomic absorption spectrometry

This paper proposes a method for the determination of lead in aluminum and magnesium antacids employing electrothermal atomic absorption spectrometry (ET AAS). The pyrolysis and atomization temperatures established during the optimization step were 700 and 2200 °C, respectively, using phosphate as the chemical modifier. Under these conditions, a characteristic mass of 25 pg, and limits of detection and quantification of 0.40 and 1.35 μg L⁻¹, respectively were obtained. Some experiments demonstrated that the calibration can be performed employing the external calibration technique using aqueous standards. The precision expressed as relative standard deviation (RSD %) was 4.03% for an antacid sample with lead concentrations of 284.5 μg L⁻¹. The proposed method was applied for the determination of lead in five antacid samples acquired in Salvador City, Brazil. The lead content was varied from 87 to 943 μg g⁻¹. The samples were also analyzed after complete dissolution by inductively coupled plasma mass spectrometry (ICP-MS). No statistical difference was observed between the results obtained by both of the procedures performed.     

Comparative study of chemical modifiers for the determination of molybdenum in milk by electrothermal atomisation atomic absorption spectrometry

A comparative study of various chemical modifiers for the determination of molybdenum in milk by electrothermal atomisation atomic absorption spectrometry was carried out. Methods with nitric acid or barium difluoride as the chemical modifier and in the absence of a chemical modifier were studied by introducing the milk samples directly into the graphite furnace with octyl alcohol. The graphite furnace programme, amount of modifier and the calibration and additions graphs were studied in all instances. The characteristic masses were 17.82, 18.64 and 12.08 pg of molybdenum in the absence of a chemical modifier and with nitric acid or barium difluoride as the chemical modifier, respectively. The precision, accuracy and interferences of the method were also investigated.     

Evaluation of different permanent modifiers for the determination of arsenic in environmental samples by electrothermal atomic absorption spectrometry

Single noble metal permanent modifiers such as, Rh, Ir, and Ru, as well as mixed tungsten plus noble metal (W-Rh, W-Ru, W-Ir) permanent modifiers thermally deposited on the integrated platform of transversally heated graphite atomizer were employed for the determination of arsenic in sludges, soils, sediments, coals, ashes and waters by electrothermal atomic absorption spectrometry. Microwave digests of solid samples and water samples were employed for obtaining the analytical characteristics of the methods with different permanent modifiers. The performance of the modifiers for arsenic determination in the real samples depended strongly on the type of permanent modifier chosen. The single noble metal (Rh, Ir and Ru) permanent modifiers were suitable for the analyte determinations in simpler matrices such as waters (recoveries of certified values 95-105%), but the analyte recoveries of certified values in sludges, soils, sediments, coals, and ashes were always lower than 90%. On the other hand, for the determination of arsenic, using W-Rh, W-Ru, and W-Ir permanent modifiers presented recoveries of certified values within 95-105% for all the samples. Long-term stability curves obtained for the determination of arsenic in environmental samples with different permanent modifiers (Rh, Ir, Ru, W-Rh, W-Ir, W-Ru) showed that the improvement in the tube lifetime depends on the tungsten deposit onto the platform. The tungsten plus noble metal permanent modifier presents a tube lifetime of at least 35% longer when compared with single permanent modifier. The results for the determination of As employing different permanent modifiers in the samples were in agreement with the certified reference materials, since no statistical differences were found after applying the paired t-test at the 95% confidence level.     

Tube-probe atomisation in electrothermal atomic absorption spectrometry

A method is described in which liquid samples are deposited by a conventional autosampler on to a tubular graphite probe positioned inside a 7.5 mm i.d. Pye Unicam SP-9 atomiser cuvette. The tube-probe has certain advantages in comparison with the flat probe systems described previously. In particular, the precision of determinations in acid media is improved since the sample solution is better confined within the atomiser and hence the effects of droplet spreading are curtailed. Also, the tube-probe is shown to reduce diffusional loss effects at high atomiser temperatures, in comparison with flat probe operation. The characteristic mass values obtained for volatile and medium volatile elements are similar for tube and flat probes. Since a greater sample volume (up to 40 μl) can be deposited and dried in the tube-probe, improved detection limits are anticipated for these elements. For more involatile elements, the greater mass of the tube-probe results in poorer sensitivity by a factor of × 3 for V and × 4 for Cr.     

Glassy carbon tubes for electrothermal atomic absorption spectrometry

Summary The use of glassy carbon as a tube material in electrothermal atomic absorption spectrometry requires modifications to the power supply if temperatures and heating rates comparable to those for graphite tubes are to be obtained. Glassy carbon tubes frequently have a longer lifetime than pyrolytic graphite coated tubes made of polycrystalline electrographite. Peak height sensitivity for glassy carbon is better by a factor of two for some volatile elements, but up to a factor of five inferior for less volatile elements than that for pyrolytic graphite coated tubes. Peak area sensitivity is generally inferior by about a factor of two. Sample volume is limited to 5–10 l because of the smooth surface.From the signal shape it can be deduced that adsorption of analyte atoms at the tube wall plays an important role in glassy carbon, and is responsible at least in part for the lower sensitivity. Non-spectral interferences can be less pronounced in glassy carbon tubes for those interferents which interact with graphite tube surfaces. Glassy carbon is, however, no alternative to pyrolytic graphite coated tubes.

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Glasartiger Kohlenstoff als Rohrmaterial für elektrothermische Atomabsorptionsspektrometrie

     

Silver and lanthanum as effective modifiers in trace determination of cadmium in nickel-base alloys by electrothermal atomic absorption spectrometry

Trace cadmium in nickel-base superalloys was determined by a stabilized temperature platform furnace using atomic absorption spectrometry with a deuterium arc background correction system. The volatility of cadmium limits the pyrolysis temperature. This prevents the removal of the interfering alloy matrix at the thermal pretreatment step. Hence, an enormously high background signal has been observed. Chemical modifiers including ammonium citrate, 1-(2-pyridylazo)-naphthol, 4-(2pyridylazo)resorcinol, 2-(5-bromo-2-pyridylazo)-5-(diethylamino)-phenol, Triton-X 100, EDTA, potassium nitrate, palladium nitrate, magnesium nitrate, aluminum chloride, ammonium dihydrogen phosphate, lanthanum oxide, lanthanum chloride and silver nitrate have been studied. Matrix interferences were effectively reduced by silver and lanthanum. The 100–300°C increase in the pyrolysis temperature effectively reduced the non-specific absorption from the alloy matrix. Interferences from foreign ions were also investigated. The merit of the proposed method was increased by the excellent agreement between the certified and the experimental values of Cd in the standard reference material, IN100, and the recovery obtained (100–104%). The precision of six successive replicate measurements was 4.9% with Ag modifier and 2.5% with La modifier, respectively. The results of analysing Tracealloy B were also satisfactory.     

Behaviour of chemical modifiers in the determination of arsenic by electrothermal atomic absorption spectrometry in petroleum products

Most comparative studies on the efficiency of chemical modifiers have been conducted in aqueous media. In the present work, we proposed a detailed study of the use of different chemical modifiers for direct determination of arsenic in complex organic matrices by electrothermal atomic absorption spectrometry (ETAAS). Palladium, rhodium, tungsten, silver, lanthanum and a mixture of palladium and magnesium were tested. The figures of merit used for evaluation and comparison were acquired in the optimal conditions for each modifier, established by multivariate optimization of the main variables based on Doehlert designs. Singular features were observed for the chemical behaviour of some modifiers in organic matrices compared to aqueous media, such as the worse performance of Pd + Mg modifier and no notice of severe tube corrosion from La application. Lanthanum was chosen as the best chemical modifier for the present application, according to predefined criteria. Lanthanum showed the minimum limit of detection, characteristic concentration and blank signal among all tested species and no effect of the concomitants usually present in petrochemical feedstocks. Using a 200 mg L⁻¹ lanthanum solution as a chemical modifier, the average relative standard deviations of 7 and 16% (at 3-15 μg L⁻¹ level) and characteristic concentrations of 0.47 and 0.77 μg L⁻¹ for naphtha and petroleum condensates, respectively, were observed.