Slurry sampling graphite furnace atomic absorption spectrometry: determination of trace metals in mineral coal

A procedure for lead, cadmium and copper determination in coal samples based on slurry sampling using an atomic absorption spectrometer equipped with a transversely heated graphite tube atomizer is proposed. The slurries were prepared by weighing the samples directly into autosampler cups (5-30 mg) and adding a 1.5 ml aliquot of a diluent mixture of 5% v/v HNO(3), 0.05% Triton X-100 and 10% ethanol. The slurry was homogenized by manual stirring before measurement. Slurry homogenization using ultrasonic agitation was also investigated for comparison. The effect of particle size and the use of different diluent compositions on the slurry preparation were investigated. The temperature programmes were optimized on the basis of pyrolysis and atomization curves. Absorbance characteristics with and without the addition of a palladium-magnesium modifier were compared. The use of 0.05% m/v Pd and 0.03% m/v Mg was found satisfactory for stabilizing Cd and Pb. The calibration was performed with aqueous standards. In addition, a conventional acid digestion procedure was applied to verify the efficiency of the slurry sampling. Better recoveries of the analytes were obtained when the particle size was reduced to <37 mum. Several certified coal reference materials (BCR Nos. 40, 180, and 181) were analyzed, and good agreement was obtained between the results from the proposed slurry sampling method and the certificate values.     

Direct solid vs. slurry analysis of tobacco leaves for some trace metals by graphite furnace AAS

Summary Graphite furnace atomic absorption spectrometry (GFAAS) is used to determine cadmium, lead, nickel and cobalt in two samples of tobacco leaves (candidate reference materials). Two techniques for the direct determination of these elements are investigated — direct solid sampling into a ring chamber tube specially designed for the Zeiss AAS-3 spectrometer and slurry sampling. For both investigated sampling methods the optimum parameters of temperature-time programs, influence of Pd modifier and calibration methods are discussed. There is acceptable agreement between the results obtained from direct solid, slurry and solution (after wet decomposition) sampling.Presented at the 4th International Colloquium on Solid Sampling with Atomic Spectroscopy, October 8–10, 1990; Jülich, Federal Republic of Germany     

The application of metal-coated graphite tubes to the determination of trace metals in biological materials: I. The determination of lead in blood using a tungsten-coated graphite tube

A new technique is introduced in trace metal determinations in biological materials by coating the graphite tube with tungsten by a highly reproducible process. This coating appeared to be responsible for the prevention of residue formation that occurred in untreated graphite tubes when lead in blood was analyzed. The life of the graphite tube was thus increased by about 300% for this matrix.     

In situ preconcentration of trace metals in high purity water onto graphite tube by multiple injections followed by graphite furnace atomic absorption spectrometry

Direct determination of trace metals at extremely low levels in high purity water is described. The method incorporates an in situ preconcentration technique in the graphite furnace of the atomic absorption spectrometer. The in situ preconcentration process involves multiple injections and evaporation in apyrocoated graphite tube. The feasibility of the proposed method of multiple injections (up to 9×90 l) prior to analysis has been investigated. A SLRS-2 certified water sample has been used for quality control, and the results are in good agreement with the certified value and with determination by standard addition method. Typically, up to 0.8 ml of sample could be analyzed. Due to the relatively large sample volume, the detection limits for the elements of interest are in the range of 3–9 ng/l.     

A new approach for fluorine determination by solid sampling graphite furnace molecular absorption spectrometry

This work deals with the determination of fluorine by solid sampling graphite furnace molecular absorption spectrometry. The molecular absorbance of aluminum monofluoride (AlF), which is produced in the vapor phase in the presence of Al³⁺, is measured at 227.5 nm, a non-resonant platinum line. A conventional graphite furnace program has been used with pyrolysis and vaporization temperatures of 800 and 2300 °C, respectively. Solutions of Ba²⁺ and Al³⁺ have been used to avoid fluorine losses during the pyrolysis stage and to produce AlF in the vaporization stage, respectively. Certified coal and alumina samples were analyzed using aqueous standards for calibration. The agreement between the found concentration and the certified value, or the value obtained by another method ranged from 92 to 105%, with a relative standard deviation less than 8.5%. The limit of detection and the characteristic mass was 0.17 μg g^− 1 and 205 pg, respectively.     

Direct determination of Ag,Cu and Ni in solid materials by graphite furnace atomic absorption spectrometry using a specially designed graphite tube

This paper presents first results of a study using a specially designed graphite tube (“ring chamber tube”) for direct solid sample analysis. This tube allowed the introduction of a relatively large amount (up to 10 mg) of solid material into a separate chamber around the middle part of the atomisation volume to avoid any disturbance of the optical light path in the atomisation volume due to the solid material. Graphite tubes without and with pyrolytic coatings have been used. Best results were obtained using low and well-defined ramp rates, long integration times and integration of the absorbance (A.s) signals. The good analytical applicability of this tube is demonstrated by several examples: Ag in gold wire for microelectronics and Cu and Ni in plant material. The results obtained from three different methods of calibration are in good agreement with the certified values. The detection limits reached for the three elements are in the pg-range.     

Application of the graphite furnace to the determination of trace iron in gold and silver

Atomic-absorption analysis using a graphite furnace is a powerful technique for the determination of nanogram amounts of iron. It can be applied to the determination of traces of iron in gold and silver. These metals may be removed from solution by reduction to metallic gold and precipitation as silver chloride respectively. Iron is not co-precipitated. The iron content can be determined in 50-100 mg of the noble metals with an error of about 7% (or 0.1 ppm).     

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

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

---

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

     

微波消解-GFAAS测定浅水湖泊底泥中重金属元素

探讨了采用微波消解作为底泥样品的前处理方法,运用石墨炉原子吸收法测定浅水湖泊底泥中Cu,Pb,Zn,Cd,Cr含量的实验条件.方法的RSD为2.0％～4.1％,平均回收率为97.4％～101.5％,Cu,Pb,Zn,Cd,Cr的检出限分别为0.4,5,2.8,0.25,2.5ng.该法适合于浅水湖泊底泥中重金属含量的测定.     

Direct determination of iron in sand using solid sampling graphite furnace atomic absorption spectrometry

A fast and reliable method for the direct determination of iron in sand by solid sampling graphite furnace atomic absorption spectrometry was developed. A Zeeman-effect 3-field background corrector was used to decrease the sensitivity of spectrometer measurements. This strategy allowed working with up to 200 μg of samples, thus improving the representativity. Using samples with small particle sizes (1–50 μm) and adding 5 μg Pd as chemical modifier, it was possible to obtain suitable calibration curves with aqueous reference solutions. The pyrolysis and atomization temperatures for the optimized heating program were 1400 and 2500 °C, respectively. The characteristic mass, based on integrated absorbance, was 56 pg, and the detection limits, calculated considering the variability of 20 consecutive measurements of platform inserted without sample was 32 pg. The accuracy of the procedure was checked with the analysis of two reference materials (IPT 62 and 63). The determined concentrations were in agreement with the recommended values (95% confidence level). Five sand samples were analyzed, and a good agreement (95% confidence level) was observed using the proposed method and conventional flame atomic absorption spectrometry. The relative standard deviations were lower than 25% (n = 5). The tube and boat platform lifetimes were around 1000 and 250 heating cycles, respectively. Correspondence: Pedro V. Oliveira, Instituto de Química, Universidade de S?o Paulo, CP 26077, 05513-970 S?o Paulo, SP, Brazil     

Determination of trace impurities in aluminum nitride by direct solid sampling graphite furnace atomic absorption spectrometry

The trace impurities Cr, Cu, Fe, K, Mn, Sb and Zn were determined in powdered aluminum nitride by direct solid sampling graphite furnace atomic absorption spectrometry using a ZEEnit 60 atomic absorption spectrometer. This spectrometer features inverse Zeeman-effect background correction and a variable magnetic field enabling measurements in two sensitivity modes over a concentration range of three orders of magnitude. The measurement sensitivity can be adjusted to the analyte concentration in the sample. The use of chemical modifiers was not necessary. Calibration was carried out by means of calibration curves obtained with aqueous standard solutions. Accuracy was checked mainly by comparison of the results with those obtained by instrumental and radiochemical neutron activation analysis whereby, excluding the results for potassium, no significant differences were found by carrying out the t-test at the significance level 0.05. The limits of detection were between 0.05 ng g⁻¹ (Zn) and 80 ng g⁻¹ (Fe) and the relative standard deviations below 11 %. With the proposed method, up to ten measurement cycles can be carried out in one hour.     

Influence of the tube surface on atomization behavior in a graphite tube furnace

Summary Sensitivity is compared for a number of elements in tubes for electrothermal atomic absorption spectrometry made from pyrolytic graphite coated and uncoated polycrystalline electrographite and from glassy carbon. The best atomization efficiency is always obtained in a pyrolytic graphite coated tube, independent of the volatility of the element and the atomization mechanism involved. The pronounced sticking properties of metal atoms to active sites of uncoated polycrystalline electrographite and glassy carbon are believed to be responsible to this behavior. This theory is supported by the observed shifts in peak maxima, peak broadening, and the higher atomization temperatures that have to be applied in these tubes. For elements forming stable carbides, these effects can be enhanced by chemical reactions with the tube material.

---

Einfluß der Rohroberfläche auf das Atomisierungsverhalten in einem Graphitrohrofen

Zusammenfassung Für eine Reihe von Elementen wird die Empfindlichkeit in Rohren für die elektrothermische Atomabsorptionsspektrometrie aus pyrolytisch beschichtetem und unbeschichtetem polykristallinem Elektrographit und aus glasartigem Kohlenstoff verglichen. Die wirksamste Atomisierung wird stets in pyrolytisch beschichteten Graphitrohren erzielt, unabhängig von der Flüchtigkeit des Elements und von dem Atomisierungsmechanismus. Wir nehmen an, daß die ausgeprägten Hafteigenschaften von Metallatomen an aktiven Stellen von polykristallinem Elektrographit und glasartigem Kohlenstoff für dieses Verhalten verantwortlich sind. Diese Theorie wird gestützt von den beobachteten Verschiebungen der Peakmaxima, Peakverbreiterungen und den höheren Atomisierungstemperaturen, die in diesen Rohren verwendet werden müssen. Für Elemente, die stabile Carbide bilden, können diese Effekte durch chemische Reaktionen mit dem Rohrmaterial noch verstärkt werden.

     

Evaluation of biological sample mineralisation methods for the determination of fluorine by graphite furnace molecular absorption spectrometry

Various mineralisation methods were evaluated as means of treating different liquid and solid biological samples for the determination of fluorine by the formation of aluminium monofluoride in an electrothermal graphite furnace and molecular absorption spectrometry (AIF-MAS). Simple sample dilution and the use of 0.01 M Al3+ + 0.01 M Sr2+ solution as a matrix modifier are sufficient to determine the fluorine content in most liquid samples, although some require the addition of 0.3 M ammonium nitrate to the matrix modifier solution in order to diminish background absorbance. In solid samples, treatment methods routinely used with fluoride ion-selective electrodes such as microdiffusion, furnace ashing - microdiffusion and oxygen flask combustion, were tested for compatibility with AIF-MAS. The results were compared with those obtained with a fluoride ion-selective electrode. The proposed mineralisation methods were checked for applicability to different plants, foodstuffs and other biological materials. Some of the methods gave an over-all precision of better than 10%, which is often acceptable, and all methods gave recoveries above 80%. Differences between labile + ionic fluoride and total fluorine can be established by sample treatment.     

Single drop microextraction combined with graphite furnace atomic absorption spectrometry for determination of lead in biological samples

Single drop microextraction combined with graphite furnace atomic absorption spectrometry is introduced for the determination of trace lead in water samples. A drop of 1-phenyl-3-methyl-4-benzoyl-5-pyrazolone (PMBP) dissolved in benzene was held at the tip of a microsyringe and immerged into the sample solution which was stirred, the solvent drop interacts with the sample solution, and the analyte was extracted into the drop and concentrated. After extracting for a period of time, the drop was retracted into the microsyringe and directly injected into graphite furnace for GFAAS determination of Pb. Several factors affecting the extraction efficiency, such as pH of sample solution, drop volume, stirring rate and extraction time, were optimized. Under the optimized conditions, an enhancement factor of 16 was achieved, and the detection limits for Pb were 25 ng L⁻¹. The relative standard deviation for seven replicate determination of 10 ng mL⁻¹ Pb was 6.1%. The method was applied to determine trace Pb in biological samples with satisfactory results. Correspondence: Pei Liang, Key Laboratory of Pesticide & Chemical Biology of Ministry of Education, College of Chemistry, Central China Normal University, Wuhan 430079, P.R. China     

Alkali metal fluoride matrix modifiers for the determination of trace levels of silicon by graphite furnace atomic absorption spectrometry

A method is described for the determination of silicon by graphite-furnace atomic absorption spectrometry with alkali metal fluorides as matrix modifiers. Alkali metal fluorides react with silicon to produce metal hexafluorosilicates, which are stable at temperatures as high as 1120– 1300°C, depending on the particular metal used. At higher temperatures, alkali metal hexafluorosilicates decompose into the metal fluoride and silicon tetrafluoride. The subsequent gas-phase atomization of silicon tetrafluoride occurs rapidly, and produces clean, sharp absorption peaks. When used in conjunction with a zirconium-treated graphite tube, this method has a sensitivity of 50 pg Si at a confidence interval of 95%. There is no evidence of silicon carbide formation in the graphite tube, and very little evidence of any deterioration of the zirconium-treated surface, as demonstrated by the fact that more than 200 samples can be processed on a single graphite tube without a decrease in sensitivity or change in the baseline.     

Comparison of standard materials for the establishment of calibration curves in solid sampling graphite furnace atomic absorption spectrometry. Direct determination of copper in powdered biological samples

Summary The selection of standard materials for the establishment of calibration curves is one of the most important problems in the direct analysis of biological samples by GFAAS. Three kinds of standard materials, NBS tomato leaves, coprecipitates with magnesium oxinate and Ni/DMG/PAN were investigated. It was found that it is possible to use both the NBS-SRM and the synthetic reference material prepared by coprecipitation with magnesium oxinate as standard materials for the direct determination of copper in several biological samples issued from NBS and NIES. However, too low results are obtained when the synthetic reference material prepared by coprecipitation with Ni/DMG/PAN is used. In order to clarify this, the effects of nickel and magnesium were examined and the role of magnesium was discussed.     

Low volume microwave digestion for the determination of selenium in marine biological tissues by graphite furnace atomic absorption spectroscopy

A microwave digestion method for the determination of marine biological tissues has been developed to allow determination of selenium in small sample sizes (< 0.1 g). The benefits of this technique include maintaining concentrates in extracts without the subsequent over dilution encountered when using larger vessels, increased sample throughput and reduced loss of volatile material. Freeze dried biological material (< 0.1 g) and nitric acid (1 ml) were placed into 7 ml screw top Teflon vessels which are completely sealed on capping. Two 7 ml vials were placed into larger 120 ml vessels fitted with a Teflon spacer and 10 ml of distilled water. The effects of microwave power and time, and sample mass on selenium recovery from three marine standard reference materials (NIST SRM 1566a Oyster Tissue, NRCC DORM-1 Dogfish Muscle and NRCC TORT-1 Lobster Hepatopancreas) were examined. The optimum conditions: 600 W, 2 min; 0 W, 2 min; 450 W, 45 min, allowed quantitative recoveries of selenium from these and three other standard reference materials (NRCC DOLT-1 Dogfish liver, NIST RM-50 Albacore tuna and IAEA MA-A-2 fish flesh). Studies on sample mass showed that the analysis of sample masses from 0.025 to 0.1 g gave selenium concentrations within the certified range. Six species of selenium: selenite, selenate, selenomethionine, selenocysteine, selenocystamine, and trimethyl selenonium were added to oyster, dogfish, and lobster tissues. Recoveries were near quantitative for all species (94–105%) except trimethyl selenonium (90–101%).     

Cloud point extraction for the determination of cadmium and lead in biological samples by graphite furnace atomic absorption spectrometry

The phase-separation phenomenon of non-ionic surfactants occurring in aqueous solution was used for the extraction of Cd and Pb from digested biological samples. After complexation with O,O-diethyldithiophosphate (DDTP) in hydrochloric acid medium, the analytes are quantitatively extracted to the phase rich in the non-ionic surfactant octylphenoxypolyethoxyethanol (Triton X-114) after centrifugation. Methanol acidified with 0.1 mol L⁻¹ HNO₃ was added to the surfactant-rich phase prior to its analysis by electrothermal atomic absorption spectrometry (ET AAS). The adopted concentrations for DDTP, Triton X-114 and hydrochloric acid were all optimized. Pyrolysis and atomization temperatures were optimized using the extracts and pyrolysis temperatures of 700 °C for both elements and atomization temperatures of 1400 and 1600 °C for cadmium and lead, respectively, were used without adding any modifier, which shows that considerable analyte stabilization is provided by the medium itself. A more detailed investigation was carried out to determine which components of the extract were responsible for the high thermal stability achieved and it revealed that the amount of DDTP added and the phosphorus content of the digested samples contributed significantly to this phenomenon. Detection limits (3σ_B) of 6 and 40 ng g⁻¹, along with enrichment factors of 129 and 18 for Cd and Pb, respectively, were achieved. The proposed procedure was applied to the analysis of five certified biological reference materials after microwave-assisted acid digestion in a mixture of H₂O₂ and HNO₃. Comparison with certified values was performed for accuracy evaluation, resulting in good agreement according to the t-test for a 95% confidence level. The high efficiency of cloud point extraction to carry out the determination of the studied analytes in complex matrices was, therefore, demonstrated.