Analytical application of 2f-wavelength modulation for isotope selective diode laser graphite furnace atomic absorption spectroscopy

Experiences in the analytical application of the 2f-wavelength modulation technique for isotope selective atomic absorption spectroscopy in a graphite furnace are reported. Experimental as well as calculated results are presented, mainly for the natural lithium isotopes. Sensitivity, linearity, and (isotope) selectivity are studied by intensity modulation and wavelength modulation. High selectivities can be attained, however, on the cost of detection power. It is shown that the method enables the measurement of lithium isotope ratios larger than 2000 by absorption in a low-pressure graphite tube atomizer. Received: 26 April 1999 / Revised: 25 June 1999 / Accepted: 30 June 1999     

Analytical application of 2f-wavelength modulation for isotope selective diode laser graphite furnace atomic absorption spectroscopy

Experiences in the analytical application of the 2f-wavelength modulation technique for isotope selective atomic absorption spectroscopy in a graphite furnace are reported. Experimental as well as calculated results are presented, mainly for the natural lithium isotopes. Sensitivity, linearity, and (isotope) selectivity are studied by intensity modulation and wavelength modulation. High selectivities can be attained, however, on the cost of detection power. It is shown that the method enables the measurement of lithium isotope ratios larger than 2000 by absorption in a low-pressure graphite tube atomizer.     

Quantitative element analysis by isotope dilution in diode laser graphite furnace atomic absorption spectrometry

The paper reviews the application of the isotope dilution technique in optical atomic absorption spectrometry by use of a low-pressure graphite tube furnace as atomizer and diode lasers as radiation sources. The principles and the methodology to obtain accurate quantitative results despite of the occurrence of interferences are presented. The successful application of different Doppler-limited and Doppler-free spectrometric techniques is also presented. The perspectives but also the limitations of this new method are discussed.     

Determination of palladium by graphite furnace atomic absorption spectroscopy without matrix matching

A graphite furnace atomic absorption spectroscopy method for the analysis of the palladium (Pd) content in bulk pharmaceutical drug substances and their intermediates prepared in aqueous solutions is extended to samples prepared in acetonitrile (ACN) and ACN-water mixtures as well to samples prepared in dimethyl sulfoxide (DMSO) and DMSO-water mixtures. The Pd content in samples solubilized in these solvents can be accurately determined with calibration established with standards prepared in aqueous solutions without matrix matching or using the method of standard additions. The validity of this method is demonstrated by spike recovery studies and by the agreement with results for the same samples prepared in these solvents, in concentrated nitric acid, and prepared by a microwave digestion system.     

Statistical investigations of interferences in graphite furnace atomic absorption spectroscopy

Summary Interferences in the flameless determination of cadmium using the HGA 72 were studied for HCl, HNO₃, H₂SO₄, HClO₄ and HF and found to be depending on different thermal pretreatment. The interferences of cations were much smaller than for anions. The results are discussed with respect to thermal stability as well as atomization rate of the compositions under investigation. Special emphasis is put upon the presence of interactions between interferents, which in some cases can be used to eliminate interferences.

---

Statistische Untersuchungen über Störungen bei der flammenlosen AtomabsorptionsspektralphotometrieII. Cadmium

Zusammenfassung Interferenzen, die bei der flammenlosen Bestimmung von Cadmium in der HGA 72 auftreten, wurden bei HCl, HNO₃, H₂SO₄, H₃PO₄, HClO₄ und HF studiert; die AbhÄngigkeit ihres Auftretens von der thermischen Vorbehandlung wird gezeigt. Interferenzen von Kationen sind kleiner. Die Ergebnisse werden im Hinblick auf die thermische StabilitÄt und die Atomisierungsgeschwindigkeit der Proben diskutiert. Besonders betont wird die Gegenwart von Wechselwirkungen zwischen Störungen, die manchmal auch benützt werden können, um Interferenzen auszuschalten.

Part I: Z. Anal. Chem. [10]     

The present and future of graphite furnace atomic absorption spectroscopy

Graphite furnace atomic absorption spectroscopy (AAS) technology has been greatly improved since the late 1970s and the new technology is now being used widely. The chief characteristic of the new technology is its remarkable freedom from interference while retaining the high sensitivity of graphite furnace AAS. Thus, an important goal of continuing furnace research is to identify interferences that persist and, by understanding the causes of residual interference, make further improvements to the system. Several background correction systems have been used.Furnace AAS remains a slow analytical technique, typically about 2 min per analyte and sample. One way to speed throughput is to use simultaneous multielement analysis although this is not easily compatible with the modern furnace. Inherently, the photometric range of furnace AAS has been more limited than, say, inductively coupled plasma but there are now ways to improve the range of furnace measurements. Alternatively, furnace emission provides a potential multielement opportunity, especially if the emission signal is enhanced with an electric discharge.The reduction in matrix interferences increases the opportunity of analyzing solid samples in the furnace. Solid samples may be handled by using well stirred aqueous slurries of finely ground materials. Flow injection analysis, already widely used with flame AAS, provides real potentiality. Perhaps the furnace AAS may become an 'absolute' technique. This will require some changes in the design of the spectrometer and electronic signal handling.     

Statistical investigations of interferences in graphite furnace atomic absorption spectroscopy

Summary Interferences in the flameless determination of lead using the HGA 72 were studied for HCl, HNO₃, H₂SO₄, H₃PO₄, HClO₄, HF and for a number of cations. In certain instances interferents in just 1000-fold concentration over lead are shown to cause deviations in the lead signal. Many of the interferences are matrix-dependent themselves and can be reduced by matrix variations. Optimization of the thermal pretreatment can be used effectively to reduce random error and/or systematic errors. The thermal stability of lead compounds in the graphite furnace was sufficient for charring procedures up to 900° C for 20 s.

---

Statistische Untersuchungen über Störungen bei der flammenlosen Atomabsorptionsspektralphotometrie

Zusammenfassung Interferenzen, die bei der flammenlosen Bestimmung von Blei in der HGA 72 auftreten, wurden bei HCl, HNO₃, H₂SO₄, H₃PO₄, HClO₄, HF und einigen Kationen studiert. In gewissen Fällen reicht ein nur 1000 facher Überschuß des Störions, um Abweichungen vom Signal des Bleistandards hervorzurufen. Da das Auftreten von Interferenzen auch oft matrixabhängig ist, können Matrixvariationen zur Unterdrückung von Interferenzen eingesetzt werden. Die Optimierung des Temperaturprogrammes wird erfolgreich zur Beeinflussung des Zufallsfehlers und/ oder systematischer Fehler herangezogen. In der Graphitrohrküvette reichte die Stabilität der Bleiverbindung aus, um beim Veraschungsschritt die Temperatur bis auf 900° C (20 s) zu steigern.

Part I: Z. Anal. Chem. [13].Part II: Z. Anal. Chem. [14].     

Statistical investigations of interferences in graphite furnace atomic absorption spectroscopy

Summary In the first part different methods for studying interferences of the time dependent signal in flameless AAS are presented with emphasis on factorial designs in experimentation as opposed to the one-factor-at-a-time approach.An example of the statistical computations necessary for interpretation of a multifactor experiment is worked out and discussed in detail with special consideration of the explanation of first-order interactions.The influence of instrumentation upon determinations in the graphite furnace is dealt with in the second part: The temperature in the graphite furnace was measured with a pyrometer, a thermocouple and a Hg-thermometer. The results obtained with the pyrometer were in good agreement with the values given by the manufacturer. The stability of the AAS system was checked and found to be sufficient for the investigation of interferences.

---

Statistische Untersuchungen über Störungen bei der flammenlosen AtomabsorptionsspektralphotometrieI. Methoden und Apparaturen

Zusammenfassung Im ersten Abschnitt werden die verschiedenen Möglichkeiten zur Untersuchung von Störungen des zeitabhängigen Signals bei der flammenlosen AAS aufgezeigt, wobei besondere Bedeutung den faktoriellen Versuchsplänen im Gegensatz zu einparametrigen Untersuchungen beigemessen wird.Ein Beispiel der statistischen Auswertung zur Interpretation eines Experiments mit mehreren Faktoren wird gebracht, und dabei besonderes Gewicht auf die Erklärung von Wechselwirkungen zwischen zwei Faktoren gelegt.Im zweiten Abschnitt werden die apparativen Einflüsse auf Messungen in der Graphitrohrküvette behandelt. Dazu wurde die Temperatur im Graphitrohr mit einem Pyrometer, einem Thermoelement und einem Quecksilberthermometer gemessen. Die Temperaturen, die mit der pyrometrischen Methode gefunden wurden, stimmen gut mit den vom Hersteller angegebenen Werten überein. Die Stabilität des AAS-Gerätes wurde überprüft: sie reicht für die Durchführung von Interferenzstudien aus.

     

Mechanism of boron atomization in graphite furnace atomic absorption spectroscopy

The mechanism of the atomization of boron and the enhancement of sensitivity by matrix modifier Sr(NO₃)₂ in graphite furnace AAS were discussed. X-ray diffraction and thermodynamic calculation were applied to study the mechanism of boron atomization with and without matrix modifier Sr(NO₃)₂. The formation of boron atom is due to the sublimation of solid boron which derived from the reduction of B₂O₃ by carbon. The enhancement of boron signal in the presence of Sr(NO₃)₂ is due to the formation of SrB₆ before atomization, which decreased the volatization losses of B₂O₃ and retarded the formation of B₄C.     

Application of ZrC-coated tubes to the determination of aluminum in serum by graphite furnace atomic absorption spectroscopy

An improved method for the determination of aluminum in serum by atomic absorption spectrometry with a graphite furnace is presented. The method is suitable for the analysis of serum samples having normal and elevated aluminum content. The serum sample can be analyzed diluted or undiluted because the selected temperatures program minimizes the matrix interferences. High temperatures are made possible by the use of graphite Zr-coated tubes. The detection limit is 0.7 μg Al/liter. The coefficient of variation is 3.2% for serum concentration of 5 μg Al/liter and 1% for serum concentration of 50 μg Al/liter.     

Determination of boron isotope ratios by Zeeman effect background correction-graphite furnace atomic absorption spectrometry

A new method for the determination of isotopic ratio of boron using Zeeman effect background correction-graphite furnace atomic absorption spectrometry with conventional atomizer and natural-boron hollow cathode source is described. The isotope-shift Zeeman effect at 208.9 nm is utilized for isotopic ratio determination. At a given concentration of total boron, the net absorbance decreases linearly with increasing ¹⁰B/¹¹B ratio. The absorbances are recorded at the field strength of 1.0 T. The isotope ratios measured by the proposed method were in good agreement with the results obtained by inductively coupled plasma-quadruple mass spectrometry or thermal ionization mass spectrometry. The present method is fairly fast and less expensive compared to the above techniques and is quite suitable for plant environments.     

石墨炉原子吸收光谱中尿的背景吸收研究

本文较详细地研究了尿背景吸收的来源, 特点和消除方法, 背景吸收波长特性和在石墨管内蒸发行为的研究表明, 尿的背景吸收主要来自氯化钠, 其次是氯化铵, 其他组份的贡献很小, 时间特性研究表明, 背景吸收大小和背景吸收曲线轮廓与原子化阶段的加热方式和原子化温度有关。还研究了应用基体改进剂和其他减小背景吸收的方法。     

Rubidium isotope measurements in solid samples by laser ablation-laser atomic absorption spectroscopy

Laser atomic absorption was used to measure the rubidium isotopes in a laser-induced plasma. An ⁸⁵Rb/⁸⁷Rb isotope ratio of 2.7±0.2 was determined in solid calcium carbonate samples. A Nd:YAG laser was used to produce the plasma on the surface of solid samples placed inside a low pressure chamber with a controlled atmosphere of 150 mtorr to 10 torr. The plasma conditions were optimized in order to provide the best sensitivity and resolution. A narrowband Ti:Sapphire laser was scanned across the 780.02-nm transition of the rubidium isotopes. The resolved isotope spectrum is shown, as well as the isotope selective calibration plots. A detection limit of 25 ppm for the individual isotopes was obtained. The optimization studies and the likely mechanisms of line broadening are discussed.     

石墨炉原子吸收法测定灵芝孢子粉中的痕量硒与锗

有机硒、锗具有抗癌，提高人体免疫的功能，已引起许多研究者的关注。灵芝孢子粉含有丰富的营养成分，如灵芝多糖，灵芝酸，腺苷，18种氨基酸及牛黄酸和特有的矿物元素等均起着奇特的功效，这些营养成分在人体中的功效同样引起许多研究者的重视^[1,2]。本文利用日立Z－8000型原子吸收光谱仪，采用石墨炉法测定有机硒、有机锗。     

The measurement of stable isotope distribution using Zeeman atomic absorption spectroscopy

The possibilities of stable isotope analysis using AAS are pointed out. The different isotopic effects occurring in optical spectra are discussed and the influence of the isotopic distribution in a sample on the line profile including broadening effects is analysed.An apparatus, based on the Zeeman scanning technique, is described, which can detect variations in the natural isotopic distribution. Measurements were carried out using the intercombination lines of Hg, Cd and Zn.     

The atomic absorption spectrometric determination of lithium isotope abundances by direct measurement of the absorbance ratio

A specially designed amplifier allows direct measurement of the absorbance ratio. The unit simultaneously monitors the attenuation of both a natural-lithium and a ⁶Li-enriched hollow-cathode lamp, which are aligned in the optical axis of the instrument. The attenuations are converted to absorbances, the ratio of which is proportional to the relative isotope abundance. The stable signals obtained permit rapid determinations at natural abundance levels, with a relative standard deviation of 3%.     

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%).     

Determination of trace vanadium in soil by cloud point extraction and graphite furnace atomic absorption spectroscopy

This work describes a new analytical procedure for trace vanadium by graphite furnace atomic absorption spectroscopy coupled to cloud point extraction (CPE) as the separation-preconcentration method. The CPE behavior of vanadium using methylene blue as complex agent and Triton X-100 as a surfactant was investigated systematically. Under the optimized conditions, the detection limit was 0.7 ng · mL⁻¹, and the relative standard deviation was 4.3% for vanadium (c = 50.0 ng · mL⁻¹, n = 5). The recovery of vanadium was in the range of 98.9–102.8%. The method was applied to the analysis of vanadium in certified reference materials and real samples. The results obtained were in good agreement with the certified values. Correspondence: Xiashi Zhu, Key Laboratory of Environmental Material and Environmental Engineering of Jiangsu province/College of Chemistry and Chemical Engineering, Yangzhou University, Yangzhou 225002, P.R. China     

Design and evaluation of an on-line microcolumn pre-concentration technique for graphite furnace atomic absorption spectrometry

Summary A simple method is described for trace element pre-concentration on a microcolumn of inner diameter 1 mm and 25 mm length. The column packed with methacrylate gel with bound 8-quinolinol groups (Spheron Oxin) is incorporated into the tip of the sampling arm of the autosampler. The sample solution, water, eluent and air streams are switched with an eight-port valve. The flow-rate at pre-concentration is about 0.14 ml/min. After washing out the residues of the sample matrix from the column, the collected elements are eluted with 1 mol/l HNO₃ directly into the graphite tube of the atomizer. The reproducibility of the method was found to be better than 5%. The method was used for the determination of Pb in NaCl.

---

Entwurf und Abschätzung einer on-line Mikrosäulen-Vorkonzentrierungstechnik für die Graphitofen-Atomabsorptionsspektrometrie

     

石墨炉原子吸收光谱法测定茶叶中的铅

采用石墨炉原子吸收光谱法测定茶叶中铅,以NH4H2PO4作为基体改进剂,提高了测定的灰化温度,消除了基体干扰.方法简便,快速,准确度高.通过对标准物质的多次测定,结果均在其保证值范围内,相对标准偏差为2.8%.对样品进行加标回收试验,回收率为96%～105%,方法检出限为0.12μg/L.