Laser ablation for aerosol deposition graphite furnace atomic absorption spectrometry

A commercially available pulse laser was used with a graphite furnace (GF) atomic absorption (AA) spectrometer for the trace analysis of metals in solid samples.Laser ablated solid material was deposited onto the inner surface of the GF. The optimum deposition temperature was 300 K. The deposited aerosol was atomized in a conventional GF heating regime.The analytical results in the deposition technique for Cd, Zn, Pb, Ag, Mn, Fe and Ni contained in different target materials were compared with results obtained with another laser ablation GF technique, which is characterized by the transport of the ablated material into a constant temperature GF with immediate atomization of the aerosol particles. The deposition technique improved the sensitivity and precision for the low volatile elements Cd, Zn and Pb. In contrast, the aerosol injection technique is preferable for the determination of elements that require more energy for atomization. Working with tube temperatures of up to 2800 K the authors obtained higher absorbance values (peak height) for Mn, Fe and Ni using the injection technique. The use of multiple deposition of laser ablated material inside the GF to achieve improved detection limits and higher precision for one atomization seems promising only for selected matrices.     

Preconcentration of analytes by aerosol deposition in Graphite Furnace Atomic Absorption Spectrometry at the pg ml−1 level

Different experimental configurations were considered, using an atomic absorption spectrometer, in order to obtain a suitable preconcentration of analyte inside the graphite furnace via aerosol deposition.The aim was to optimize the procedure in order to measure concentrations down to 1–5 pg ml⁻¹ in matrices with a low chemical content, such as snow or ice. At these concentration levels, the risk of contaminating the sample is one of the main problems to be considered when designing the aerosol deposition set-up. In addition, since the deposition time (t_dep) may be up to several tens of minutes, all the parameters which are decisive in controlling both deposition and atomization steps must be time independent and show good repeatability among measurements.With the procedure proposed in this paper it was found that the absorbance was linearly dependent on the product C_s·t_dep, where C, is the analyte concentration in the sample solution, down to the pg ml⁻¹ level. The regression parameters of the calibration curve were found to be reproducible for a period of weeks, indicating that the instrumental variables presented a high repeatability and, in particular, that the yield of atoms per unit mass in the sample was not influenced by the life-time of the graphite furnace (usually about 1000 firings).At a concentration of 3 pg ml⁻¹ of cadmium, the coefficient of variation of the absorbance (5 replicates) was found to be as low as 3 – 5%, when a 15 min deposition time was applied. At this concentration, the overall sample standard deviation, which depends on all the steps from sampling to analysis, remains the most significant figure of merit.     

Solid sampling by electrothermal vaporization in combination with electrostatic particle deposition for electrothermal atomization multi-element analysis

A novel combination of electrothermal sample vaporization from one furnace and electrostatic deposition of the aerosol on a L'vov platform in a second graphite furnace used for subsequent electrothermal atomization multi-element analysis is described. The aerosol generated by vaporization of liquid as well as solid primary samples is transported to the graphite furnace by an Ar gas flow and is piped into the furnace through the dosing hole via a glass capillary mounted on the autosampler arm of a continuum source coherent forward scattering spectrometer. The deposition on the graphite platform is obtained electrostatically by a corona-like discharge. The near quantitative deposition of the produced and transported aerosol allows optimal direct determination of the transport efficiencies by comparing the signals obtained by measuring liquid samples directly with the spectrometer with signals obtained with samples transferred with electrothermal vaporization and electrostatic deposition. Over all transfer efficiencies up to 30% are observed with liquid primary samples. Results obtained with solid sampling of BCR CRM 189 Wholemeal flour are in good agreement with the certified values.     

The application of electrodeposition on a tungsten wire to furnace atomic absorption spectrometry

This work utilizes electrolytic separation and preconcentration of analyte metals on a thin tungsten wire electrode prior to their determination by furnace atomic absorption spectrometry (AAS). Only a very basic electrolysis system operating at constant applied voltages is needed. Following the deposition step, the wire electrode is inserted into the central region of a miniature CRA 90 furnace and electodeposited metals atomized. Tungsten wire melts in the furnace environment at approximately 2500°C and this restricts the range of metals which can be determined by this technique. So far, elements characterized by relatively low atomization temperatures, such as Cd, Zn, Ag, Pb and Cu, have been studied. Sensitivity improvements ranging from 1.5 to 15-fold over the conventional furnace AAS have been achieved with deposition times between 30 and 300 s. No appreciable background absorption has resulted during the atomization step following depositions from NaCl solutions, confirming very efficient separation. The technique has been successfully applied to the determinations of Pb in blood digest and in seawater. Apart from the analytical applications, the wire deposition approach to furnace atomization offers some more fundamental advantages over systems operated in the conventional manner. It can be used to study the atomization behaviour of elements in metallic form in relation to the atomization of their different compounds. Moreover, by rapidly introducing the wire into the furnace preheated to a constant temperature, very fast atomization is achieved with corresponding improvements in analytical sensitivities. The rapid wire introduction technique also lends itself to studies of the removal of sample vapour from furnaces.     

Online deposition of nano‐aerosol for matrix‐assisted laser desorption/ionization mass spectrometry

An online nano‐aerosol sample deposition method for matrix‐assisted laser desorption/ionization (MALDI) mass spectrometry is described in which matrix and analyte particles between 50 and 500 nm are aerodynamically focused onto a tight spot, ca. 200 µm in diameter, on the target plate under vacuum. MALDI analysis of the target is performed without additional sample preparation. The method is evaluated with insulin as the analyte and alpha‐cyano‐4‐hydroxycinnamic acid (CHCA) as the matrix. Two preparation modes are compared with conventional dried‐droplet deposition: mixture deposition where a single layer is deposited consisting of particles that contain both matrix and analyte, and layered deposition where an underlayer of matrix particles and an overlayer of analyte particles are deposited separately. Desalting is performed by adding ammonium sulfate to the solution used to generate the matrix aerosol. With mixture deposition, the optimum matrix‐to‐analyte mole ratio is about 500:1 compared with 5000:1 for the conventional dried‐droplet method. With layered deposition, the thicknesses of the matrix and analyte layers are more important determinants of the analyte signal intensity than the matrix‐to‐analyte mole ratio. Analyte signal intensities are independent of matrix layer thickness above 200 nm, and the optimum analyte signal is obtained with an analyte layer thickness of about 100 nm. Copyright © 2009 John Wiley & Sons, Ltd.     

Investigation of an Aerosol Deposition Technique for Sample Introduction for the Determination of Manganese by Electrothermal Atomization Atomic Absorption Spectrometry

Abstract

An aerosol deposition technique for sample introduction for the determination of manganese by electrothermal atomization atomic absorption spectrometry is described and evaluated. A calibration between deposit time and injected volume of sample can be constructed. The analytical charecteristic concentration can be increased significantly by increasing the deposition time for samples of low matrix concentration.     

Condensation of analyte vapor species in graphite furnace atomic absorption spectrometry

A shadow spectral digital imaging technique (SSDI) with charge coupled device (CCD) camera detection was used to investigate the spatial and temporal distribution of condensation clouds of analyte species generated in a graphite furnace during the atomization of 5–40-μg masses of metals. Complex, non-uniform structures of aerosol species located away from both the graphite tube axis and walls are prevalent. Species giving rise to observed signals are likely clusters of metals in the case of Ag, Au and Pd, and oxide aerosols for elements such as Al, Ca and Mg. Source scatter often arises during the atomization of relatively large masses of analytes (or during the atomization of real samples containing high concentrations of concomitant matrix species) in the graphite furnace due to such aerosol formation. The SSDI technique is an extremely useful aid to the elucidation of this phenomenon and imaging at several wavelengths using both line and continuum sources in combination with (thermal, incandescent) emission from these structures permits a more complete picture to be developed.     

Temporal Variations in Gas Temperature in an Atomization Stage of Cadmium and Tellurium Evaluated by Using the Two-line Method in Graphite Furnace Atomic Absorption Spectrometry

In order to discuss the atomization process of an analyte element occurring in a graphite furnace for atomic absorption spectrometry, we measured variations in the characteristic temperature with the progress of an atomization stage, by using a two-line method under the assumption of a Boltzmann distribution. For this purpose, iron was chosen as the analyte element. Also, the atomic absorption of two iron atomic lines, Fe I 372.0 nm and Fe I 373.7 nm, was simultaneously monitored as a probe for the temperature determination. This method enables variations in the gas temperature to be directly traced, yielding a temperature distribution closely related to the diffusion behavior of the probe element in the furnace. This temperature variation was very different from the furnace wall temperatures, which were monitored in conventional temperature control for atomic absorption spectrometry. Correlations between the gas temperature and the charring/atomizing temperatures in the heating program of the furnace were investigated. The atomization of cadmium and tellurium was also investigated by a comparison between the gas temperature with the wall temperature of the furnace. The atomic absorption of cadmium or tellurium appeared to be apart from the absorption of iron while the gas temperature was still low. Therefore, the analyte atoms could be atomized through direct contact with the wall of the graphite furnace, which has a much higher temperature compared to the gas atmosphere during atomization. Their atomization would be caused by conductive heating from the furnace wall rather than by radiant heating in the furnace.     

Coupled in situ electrodeposition-electrothermal atomic absorption spectrometry: a new approach in quantitative matrix free analysis

A new approach for in situ matrix elimination in electrothermal atomic absorption spectroscopy (ETAAS) is described. In an initial electrodeposition step (possible by use of a Pt/Ir delivery tube on the autosampler) the furnace is coated with about 0.25 μg Pd. Quantitative deposition of metallic analytes onto this renewable substrate is achieved from 25–40 μl samples by electrolysis for 60 s at 3.5–5.0 V (35–45 mA). Reprogramming of the autosampler to remove spent electrolyte after the electrolyses and to provide a rinse cycle facilitates removal of > 99.5% of a 0.5 M NaCl matrix prior to atomization. It is proposed that the analyte is bound onto the metallic modifier, rather than encapsulated within it. Binding of the analyte with Pd significantly increases the appearance temperature for Cd and Pb. The ashing loss for these analytes deposited onto Pd from a Cl⁻ matrix is observed above 900°C and 1300°C, respectively. This stabilization facilitates separation of the residual NaCl matrix before atomization. It has been established for Cd that sensitivity of the determination remains constant for matrices as diverse as 1% HNO₃, 0.5 M NaCl and sea water.     

The gas temperature in and the gas expulsion from a graphite furnace used for atomic absorption spectrometry

A simplified model for heat transfer based on thermal conduction is used to calculate the radial gas temperature distribution inside a semi-enclosed, commercial graphite tube furnace used for atomic absorption spectrometry. In the absence of a forced convective flow of a purge gas, the gas temperature inside the graphite furnace during its heating is lower than the wall temperature. After the wall temperature has attained a steady-state value, the gas temperature approaches the wall temperature and the radial temperature gradient in the gas decreases. The difference between the wall temperature and the gas temperature depends on the temperature program used, the thermal properties of the purge gas, and the atomizer geometry. The residence time of relatively volatile analyte elements is largely controlled by expulsion when wall atomization at high heating rates and high atomization temperatures are used. Analytical sensitivities are often enhanced by vaporizing the analyte into a gas having an approximately constant temperature.     

Low-temperature migration of lead,thallium, and selenium onto a palladium modifier during the analysis of solutions and slurries by electrothermal atomic absorption spectrometry

A palladium/magnesium modifier, when premixed with solutions or slurries, stabilizes many analytes to higher pyrolysis and atomization temperatures. Similar behavior was seen when analyte and modifier were physically separated by pipetting them onto opposite sides of a L'vov platform. During the pyrolysis stage of the furnace heating cycle, lead, thallium, and selenium migrated from the platform surface and interacted with the modifier on the opposite side. This behavior explains the consistent stabilization by palladium of analytes in slurry samples. Under conventional operating conditions the modifier is premixed with the slurry, and on drying in the furnace, the analyte and modifier may not make close contact. However, this is unimportant since the analyte will migrate to the palladium on heating. Then the rate-limiting step leading to atomization is the release of analyte from palladium, and it is the same for solutions and slurries. Therefore, aqueous standards can be used for slurry analysis.     

Tungsten atomizer--theory of atomization mechanism of some volatile analytes

Several types of chemical reactions may participate in the evolution of free atoms in a tungsten furnace. Reactions may take place either in the homogeneous or heterogeneous phase. The assumed reactions may be classified into four types according to the phases in which they take place. Reactions occurring in the gaseous phase, i.e. in the inner volume of the furnace, are kinetically more significant. However, for atomization of easily volatile analytes heterogeneous reaction between gaseous compounds and between condensed salts of analytes and the solid surface of the furnace become significant. With regards to the reaction mechanisms during drying, pyrolysis and atomization of nitrates of volatile analytes, three basic types of chemical reactions may be assumed. Free atoms of analytes arise by evaporation of the elementary form of analytes at atomization temperature, where the particular analyte in its elementary form is produced by direct reduction of analyte nitrate by tungsten or by hydrogen at higher temperatures. Precursory reactions of atom formation are reduction reactions which occur between analyte nitrates and tungsten, between analyte nitrates and hydrogen, as well as reactions of thermal dissociation of relevant nitrates. The importance of particular types of precursory reactions for formation of metallic analytes or their oxides is documented by dependence of Gibbs energy values of particular reactions on the temperature.     

Tungsten atomizer – theory of atomization mechanism of some volatile analytes

Several types of chemical reactions may participate in the evolution of free atoms in a tungsten furnace. Reactions may take place either in the homogeneous or heterogeneous phase. The assumed reactions may be classified into four types according to the phases in which they take place. Reactions occurring in the gaseous phase, i.e. in the inner volume of the furnace, are kinetically more significant. However, for atomization of easily volatile analytes heterogeneous reaction between gaseous compounds and between condensed salts of analytes and the solid surface of the furnace become significant. With regards to the reaction mechanisms during drying, pyrolysis and atomization of nitrates of volatile analytes, three basic types of chemical reactions may be assumed. Free atoms of analytes arise by evaporation of the elementary form of analytes at atomization temperature, where the particular analyte in its elementary form is produced by direct reduction of analyte nitrate by tungsten or by hydrogen at higher temperatures. Precursory reactions of atom formation are reduction reactions which occur between analyte nitrates and tungsten, between analyte nitrates and hydrogen, as well as reactions of thermal dissociation of relevant nitrates. The importance of particular types of precursory reactions for formation of metallic analytes or their oxides is documented by dependence of Gibbs energy values of particular reactions on the temperature.     

Multi-element determination with solid sampling by laser ablation using electrothermal atomisation and continuum source coherent forward scattering spectrometry

Laser ablation allows fast and easy sampling of solids with a spatial resolution of some (μm vertical and some 30 μm lateral. The deposition of the laser generated aerosol in a graphite furnace in combination with continuum source CFS allows simultaneous multi-element analysis and the use of internal standards. The aerosol is transported into the graphite furnace with the inert gas flow and deposited by means of a corona discharge inside the tube. The deposition efficiency shows an enhancement by about three orders of magnitude, compared to the deposition without a field. The analytical precision and accuracy has been tested with metals and mineral samples as glassy cinder from a waste incineration plant.     

A Thermo-Chemical Reactor for analytical atomic spectrometry

A novel atomization/vaporization system for analytical atomic spectrometry is developed. It consists of two electrically and thermally separated parts that can be heated separately. Unlike conventional electrothermal atomizers in which atomization occurs immediately above the vaporization site and at the same instant of time, the proposed system allows analyte atomization via an intermediate stage of fractional condensation as a two stage process: Vaporization → Condensation → Atomization. The condensation step is selective since vaporized matrix constituents are mainly non-condensable gases and leave the system by diffusion while analyte species are trapped on the cold surface of a condenser. This kind of sample distillation keeps all the advantages of traditional electrothermal atomization and allows significant reduction of matrix interferences. Integration into one design a vaporizer, condenser and atomizer gives much more flexibility for in situ sample treatment and thus the system is called a Thermo-Chemical Reactor (TCR).     

A technique coupling the analyte electrodeposition followed by in-situ stripping with electrothermal atomic absorption spectrometry for analysis of samples with high NaCl contents

A technique coupling the analyte electrodeposition followed by in-situ stripping with electrothermal atomic absorption spectrometry has been developed for determination of lead and cadmium in samples with high salt contents. To separate the analyte from the sample matrix, the analyte was in-situ quantitatively electrodeposited on a platinum sampling capillary serving as the cathode (sample volume, 20 μL). The spent electrolyte containing the sample matrix was then withdrawn, the capillary with the analyte deposited was washed with deionized water and the analyte was stripped into a chemically simple electrolyte (5 g/L NH₄H₂PO₄) by reversing the polarity of the electrodeposition circuit. Electrothermal atomization using a suitable optimized temperature program followed.     

The graphite probe constant temperature furnace

A graphite probe, on which the sample is deposited, is thrust into a heated graphite furnace tube, providing a constant temperature furnace environment. By comparison with wall sampling, the graphite probe system provides equal or improved sensitivity and detection limit and considerably less memory effect. Experiments with metals that range from volatile to refractory show that the peak width is the same at the same atomization temperature. A tube was designed that provided a curtain of argon to limit the absorbance path to about 15 mm.     

Coupling of ultrasonic nebulization to flame furnace atomic absorption spectrometry—new possibilities for trace element determination

The use of ultrasonic nebulization (USN) with desolvation system for sample introduction in flame atomic absorption spectrometry (F AAS) and flame furnace atomic absorption spectrometry (FF AAS) with a nickel tube is described. Polytetrafluorethylene (PTFE) adaptors were built to replace the pneumatic nebulizer for USN-F AAS measurements. For USN-FF AAS analysis, an alumina injector allowed the direct introduction of the dry aerosol into the nickel tube. The analytical performance of both systems is shown for Ag, Bi, Cd, Cr, Cu, Mn, Pb, Sb, Se, Tl and Zn. The results demonstrate that a sensitivity gain of up to 39 times can be achieved using USN-FF AAS, mainly due to the increase in residence time and to the absence of dilution of the analyte by the flame gases, as the atomization takes place inside the nickel tube. However, elements that require higher atomization temperatures, such as Cr and Mn, are more efficiently determined using USN-F AAS. To evaluate the accuracy of the proposed methods for the determination of trace elements, five certified reference samples were analyzed, and good agreement was, in general, achieved between certified and determined values at a 95% confidence level. The relative standard deviation was frequently below 5%, demonstrating good precision, particularly for USN-FF AAS. In this sense, coupling of USN with F AAS and especially with FF AAS has proved to be simple, safe, with high precision and good accuracy, also maintaining some of the most important features of F AAS, such as the high analytical frequency and the low running cost.     

Nickel chloride interferences on zinc and cobalt in graphite furnace atomic absorption spectrometry using a dual cavity platform

The interference mechanisms of nickel chloride in the determination of cobalt and zinc by graphite furnace atomic absorption spectrometry were investigated using a dual cavity platform. This platform, which has two separate cavities instead of one, allows interferences in the gas phase and in the condensed phase to be differentiated by pipetting the analyte and the interferent onto the separate locations as necessary. The interference mechanism of nickel chloride is found to depend upon the pyrolysis temperature. In the presence of excess nickel chloride, analyte chlorides are formed both in the condensed phase and by reaction between analyte species and HCl(g) generated by the hydrolysis of nickel chloride. The analyte chlorides are then lost during pyrolysis or at the very beginning of the atomization step. At low pyrolysis temperatures, where nickel chloride is not significantly hydrolysed, the drop in sensitivity can be attributed to the expulsion of the analyte species together with rapidly expanding decomposition products of nickel chloride, and/or to gas-phase reaction between analyte atoms and chlorine in the atomization step.