Laser-excited atomic-fluorescence spectrometry in an electrothermal atomizer with Zeeman background correction

A pulsed excimer-pumped dye laser was used to excite atomic flourescence in graphite tube electrothermal atomizer. A 60-Hz ac magnitude field was applied around the atomizer and parallel to the excitation beam, for Zeeman background correction. The correction system was found to degrade the detection limits for silver, cobalt, indium, manganese, lead, and thallium by a factor of between 1 and 10. An increase in magnetic field strength, or a decrease in laser linewidth, should improve the detection limits, but was not possible here. For copper, the application of Zeeman background correction was unsuccessfull because the instrumentation was unable to resolve the sigma components from the laser emission profile sufficiently during the background correction measurement. For elements that exhibit sufficient Zeeman splitting, the linear dynamic range was the same with or without background correction Zeeman background correction was used to correct for scatter, in the resonance flourescence determination of manganese in a zinc chloride matrix and in mouse brain tissue.     

An application of the Zeeman elect to atomic absorption spectrometry: Development of spectral-line sources stable in magnetic field

A new atomic-absorption spectrophotometer using the Zeeman effect, in which the magnetic field is applied to the light source, is described. A steady magnetic field of 3.8 kG was applied to conventional hollow-cathode lamps, which were operated using a high frequency power of 100 MHz.The π-and σ-components of the Zeeman split atomic lines were observed alternatively after traversing a flame. The absorbance difference between of the two Zeeman components was proportional to the atomic-absorption and was not influenced by background absorption. Dependences of atomic absorption signals on magnetic field strengths which were in close relation to profiles of absorption lines were measured for elements Cd, Mg, Pb, Cr, Cu and Mn by scanning of magnetic field strength.     

Investigation of the feasibility to use Zeeman-effect background correction for the graphite furnace determination of phosphorus using high-resolution continuum source atomic absorption spectrometry as a diagnostic tool

The determination of phosphorus by graphite furnace atomic absorption spectrometry at the non-resonance line at 213.6 nm, and the capability of Zeeman-effect background correction (Z-BC) to deal with the fine-structured background absorption due to the PO molecule have been investigated in the presence of selected chemical modifiers. Two line source atomic absorption spectrometers, one with a longitudinally heated and the other with a transversely heated graphite tube atomizer have been used in this study, as well as two prototype high-resolution continuum source atomic absorption spectrometers, one of which had a longitudinally arranged magnet at the furnace. It has been found that Z-BC is capable correcting very well the background caused by the PO molecule, and also that of the NO molecule, which has been encountered when the Pd + Ca mixed modifier was used. Both spectra exhibited some Zeeman splitting, which, however, did not cause any artifacts or correction errors. The practical significance of this study is to confirm that accurate results can be obtained for the determination of phosphorus using Z-BC.     

An application of the Zeeman effect to atomic absorption spectrometry: a new method for background correction

A new Zeeman method for background correction in atomic absorption spectrometry was studied. The light source was operated in a steady magnetic field,     

Spectral interferences and background overcompensation in zeeman-corrected atomic absorption spectrometry : Part 1. The effect of iron on 30 elements and 49 element lines

The background compensation performance of a Zeeman corrector with the magnetic field acting on the graphite atomization cell was assessed for 30 elements and 49 element lines in an iron matrix. Two of the elements studied, gallium and zinc, are influenced by background overcompensation which introduces serious negative systematic errors. The overcompensation is due to the presence of iron lines close to the 287.4-nm gallium line and the 213.9-nm zinc line; when the magnetic field is on, the σ-components of the adjacent iron lines overlap at the position of the analyte line and a background, which is not present when the magnetic field is off, is recorded. When gallium and zinc are measured under the same conditions but with deuterium arc background correction, the adjacent iron lines cause positive systematic errors. These spectral interferences for gallium in the presence of iron can be avoided by doing the measurements at the 294.4-nm gallium line; the two lines have about the same sensitivity. When zinc is to be measured at the 213.9-nm line, with either type of background correction, the spectral interferences from iron can be avoided by careful selection of the graphite-furnace parameters. In addition to spectral interferences, iron also affects the sensitivity for both gallium and zinc.     

Separative column atomizer for the direct determination of trace amounts of volatile elements by atomic absorption spectrometry

A novel atomizer effective for direct analysis was developed using a new type separative column atomizer (SCA) module. The SCA module incorporated an atomization part, a separation column and/or reaction column part and observation windows for atomic spectroscopic measurement. This module was applied to the direct analysis of trace amounts of mercury and cadmium in practical samples. No background absorption was observed on the thermal decomposition of synthesized samples in a starch matrix and human hair at the wavelengths of the analytical lines of Hg and Cd. The effectiveness of the technique for the determination of elemental compositions is evaluated.     

A novel method for atomic absorption spectroscopy based on the analyte-Zeeman effect

A new type of atomic absorption spectrometry using the Zeeman effect of sample materials is proposed. A magnetic field was applied to the sample vapor in the direction perpendicular to the propagation of light emitted from an atomic spectral source. Absorption of radiation polarized perpendicular and parallel to the magnetic field was observed alternatively. The absorption difference was proportional to the true atomic absorption, and was not interfered with by any other molecular absorption and light scattering, i.e., background absorption. The background absorption could be monitored at exactly the same wavelength as an atomic absorption line. Suitable magnetic field strength was found for each line of the various elements.     

A simple,low cost,multielement atomic absorption spectrometer with a tungsten coil atomizer

An inexpensive, multielement atomic absorption spectrometer utilizing a tungsten coil atomizer has been developed. The novel optical arrangement employs three 60° beam combiners to blend the spectral output from four light sources such as electrodeless discharge lamps, or hollow cathode lamps, and then direct that output over an atomizer. This instrument uses an inexpensive tungsten coil atomizer that is extracted from a standard 150 W projector bulb. The temperature of the coil is computer-controlled by changing the voltage across the coil. A low voltage is first used to dry the sample then a higher voltage is used to atomize the sample. Simultaneous detection of the analyte absorption signals is accomplished using a charge-coupled device. The elements of interest in this study were Cd, Pb, and Cu. Near-line background correction was used to correct for nonspecific analyte absorption.     

Zeeman atomic absorption spectrometry

The shift of atomic spectral lines in a magnetic field (the Zeeman effect) forms the basis for three novel developments in atomic absorption spectrometry: (i) greatly improved background correction; (ii) the use of forward scattering techniques as an analytical tool; (iii) the determination of small gaseous molecules.     

Construction and performance of an a.c. modulated magnet for Zeeman atomic absorption spectroscopy

A Zeeman atomic absorption spectroscopy system has been constructed utilizing a 50 Hz sine wave modulated magnetic field that can be directed either parallel or perpendicular to the optical axis. The amplitude of the magnetic field strength is adjustable up to 10 kG at a maximum power consumption of 0.7 kW.The readout system allows normal atomic absorption as well as d.c. and a.c. Zeeman atomic absorption measurements. Plots of experimental sensitivity vs magnetic field strength and analytical curves are in agreement with theoretical predictions.Experiments in the presence of filter simulated and real background absorbance show that the described Zeeman instrument is capable of correcting background absorption up to two absorbance units.     

Determination of aluminum in highly concentrated iron samples: Study of interferences using high-resolution continuum source atomic absorption spectrometry

High-resolution continuum source atomic absorption spectrometry (HR-CS AAS) has been used to investigate spectral and non-spectral interferences found with a conventional line source atomic absorption spectrometer in the determination of aluminum in pharmaceutical products containing elevated iron and sugar concentrations. A transversely heated graphite furnace was used as the atomizer in both spectrometers. The two most sensitive aluminum lines at 309.3 nm and 396.2 nm were investigated and it was found that an iron absorption line at 309.278 nm, in the vicinity of the aluminum line at 309.271 nm, could be responsible for some spectral interference. The simultaneous presence of iron and the organic components of the matrix were responsible for radiation scattering, causing high continuous and also structured background absorption at both wavelengths. The aluminum and iron absorption could not be separated in time, i.e., the iron interference could not be eliminated by optimizing the graphite furnace temperature program. However, an interference-free determination of aluminum was possible carrying out the measurements with HR-CS AAS at 396.152 nm after applying least squares background correction for the elimination of the structured background. Analytical working range and other figures of merit were determined and are presented for both wavelengths using peak volume registration (center pixel ± 1) and the center pixel only. Limits of detection and characteristic masses ranged from 1.1 to 2.5 pg and 13 to 43 pg, respectively. The method was used for the determination of the aluminum contamination in pharmaceutical formulations for iron deficiency treatment, which present iron concentrations from 10 to 50 g l^− 1. Spike recoveries from 89% to 105% show that the proposed method can be satisfactorily used for the quality control of these formulations.     

Correction for background absorption and stray radiation in a.c. modulated Zeeman atomic absorption spectrometry

Analytical results are presented obtained with Zeeman atomic absorption (ZAA) using a modified sine wave magnetic field. The measurement at zero field strength is lengthened to 0.5 ms for a 50 Hz magnetic field of 10 kG.The a.c. Zeeman system is extended with an additional intensity measurement performed at an intermediate field strength. The three field Zeeman system (3FZAA) permits simultaneous correction for background absorption and stray radiation at the expense of halved analytical sensitivity. The background correction capabilities of ZAA and 3FZAA are the same. However, the 3FZAA signals show increased noise in comparison to ZAA.In the three field system the roll-over problem, inherent in existing Zeeman systems, is shifted to higher concentration and to higher absorbance. The height and the position of the maximum in ZAA and 3FZAA analytical curves do not depend on the amount of background absorption.A method for the extension of analytical curves in AA is presented. Utilizing an a.c. modulated magnetic field any sensitivity between zero and ordinary AA sensitivity can be obtained.     

Atomization of Al in a tungsten coil electrothermal atomic absorption spectrophotometer

Electrothermal atomic absorption spectrophotometry of Al in a tungsten coil atomizer was evaluated and applied for its determination in hemodialysis fluid. The system was mounted on a Varian Spectra AA-40 spectrophotometer with continuum background correction and all measurements, in peak height absorbance, were done at 309.3 nm. The purge gas was a mixture of 90% Ar plus 10% H(2). Observation height, gas flow, drying, pyrolysis and atomization steps were optimized. The heating program was carried out by employing a heating cycle in four steps: dry, pyrolysis, atomization and clean. The determination of Al in hemodialysis solutions was performed by using a matrix-matching procedure. Al in hemodialysis solutions was determined by TCA and by electrothermal atomization with a graphite tube atomizer. There is no differences between results obtained by both methods at a confidence level of 95%. The characteristic mass of Al by using the TCA was 39 pg and the detection limit was 2.0 mug l(-1).     

Comparative Study of the Effect of Sample Matrix on the Atomic Absorption of High-Volatile Elements in Two-Step and Conventional Atomizers

The space–time dynamics of absorbing atomic layers of cadmium and lead and molecular layers of zinc chloride in a commercially produced transverse-heated graphite atomizer and a newly developed two-step atomizer was studied. It was shown that the limiting temperature of cadmium pyrolysis in the two-step atomizer without the use of modifiers may be as high as 1000°C, whereas in the commercial analyzer is it not higher than 300°C. Levels of nonselective absorption due to sodium chloride were compared. It was found that, for a two-step atomizer, the maximum allowable mass of sodium chloride for which the background at lead and cadmium lines can be adequately compensated is 17–30 times higher than that for the commercial atomizer. The atomization of cadmium in the presence of sodium chloride was studied using time, space, and spectral resolution. It was shown that the effect of the chloride matrix in the two-step atomizer is suppressed because of sample fractionation and distillation in the course of its evaporation and condensation.     

Spectral interferences and background overcompensation in inverse zeeman-corrected atomic absorption spectrometry : Part 2. The effects of cobalt,manganese and nickel on 30 elements and 53 elements lines

The background compensation performance of a transversal alternating-current Zeeman corrector system with the magnet acting on the graphite atomization cell was assessed for 30 elements and 53 element lines in the presence of relatively large amounts of cobalt, manganese or nicke. The study reveaaled three cases of background overcompensation, all being caused by a cobalt line adjacent to the analytical line. When the magnetic field is on (and the background is measured), a σ-component of the cobalt lines overlaps the emission lines of boron (249.7 nm), mercury (253.7nm) and gold (267.6 nm). The interfering effect on boron is small, but mercury and gold are more seriously affected; for both elements a serious negative systematic error is introduced. Manganese and nickel did not give any overcompensation effects on the elements and lines studied. When gold and mercury were measured with the use of the same experimental parameters and a conventional deuterium-arc background corrector, only mercury suffered from spectral interference. The spectral interference of cobalt on mercury, with either type of background correction, can be avoided by selecting a proper furnace program. When gold is tobe measured in the presence of cobalt and with the present Zeeman background-correction system, the 267.6.-nm line should not be used; the more sensitive 242.8 nm line is recommended.     

Polarized Zeeman effect atomic absorption spectrophotometry using a flame atomizer

A static magnetic field at 10 kG$\text{\$}\text{?}$was applied to a 10cm laminar flame produced by a premix type burner, and absorptions were observed for the polarized components of the radiation from a hollow cathode lamp. The dynamic range of the measurement was 10⁴–10⁵ for typical elements.The results showed that (1) the optimal conditions for double beam measurement and accurate correction of background absorption are achieved at the same time, (2) even if the flame conditions and the light intensity are changed, the baseline is not shifted, (3) the flame fluctuation noise and the lamp flicker noise are reduced, and (4) background absorption is corrected exactly at the same wavelength as the atomic absorption line.We thus concluded that the feasibility of flame atomic absorption spectrophotometry is much improved with this technique.     

Evaluation of electrodeposited tungsten chemical modifier for direct determination of chromium in urine by ETAAS

The direct determination of chromium in urine by electrothermal atomic absorption spectrometry (ETAAS) using graphite tubes modified with tungsten is proposed. Modification of the graphite is made by tungsten electrodeposition over the whole surface atomizer followed by carbide formation by heating the tube inside its own furnace. For tungsten electrocoating, the graphite tube and a platinum electrode were connected to a power supply as cathode and anode, respectively, and immersed in a solution containing 2 mg of W in 0.1% v/v HNO₃. Then, 5 V was applied between the electrodes during 20 min for tungsten electrodeposition over the whole atomizer. A SpectrAA 220 Varian atomic absorption spectrometer equipped with a deuterium background corrector was used throughout. Undiluted urine (20 μl) was delivered over the tungsten-treated tube and the chromium-integrated absorbance was measured after applying a suitable heating program with maximum pyrolysis at 1300 °C and atomization at 2500 °C. With electrodeposited tungsten modifier, the tube lifetime increased up to four times when compared to previous published methods for Cr determination in urine by ETAAS, reaching 800 firings. Method detection limit (3 S.D.) was 0.10 μg l⁻¹, based on 10 integrated absorbance measurements of a urine sample with low Cr concentration. Two reference materials of urines (SRM 2670) from National Institute of Standards and Technology (NIST) were analyzed for method validation. For additional validation, results obtained from eight human urine samples were also analyzed in a spectrometer with Zeeman effect background correction.     

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.     

Frequency-modulated simultaneous multielement atomic absorption spectrometry using electrothermal atomizer and deuterium background correction

Characteristic data of the frequency-modulated simultaneous multielement atomic absorption spectrometry (FREMSAAS) using electrothermal atomizer with deuterium background correction, have been determined. The data obtained have been processed by using several statistical tests recommended for quality control purposes. The instrumentation has been presented as well as procedures of separating elements into measure groups and fixing of variable conditions. Detection limits, characteristic masses and working ranges have been given for the eleven elements examined. The data have been in good agreement to results obtained with conventional one-channel AAS instruments. The eleven elements have been simultaneously determined in a standard reference material (SRM) and all results are compatible with a 95% certainty with the certified values. FREMSAAS has been applied to a real sample.Dedicated to Professor Dr. Dieter-Klockow on the occasion of his 60th birthday