Matrix atomization atomic absorption

When the identity of the matrix interference is unknown, or when it is impossible to adjust the flame to eliminate the interference, then other means must be used to compensate for the background interference. Several methods have been developed to compensate for matrix interferences, and most atomic absorption spectrophotometers include one or more of these methods. 

In atomic absorption spectroscopy, the correction of the net absorbance from that due to the sample matrix. 

Electrothermal vaporization can be used for 5-100 )iL sample solution volumes or for small amounts of some solids. A graphite furnace similar to those used for graphite-furnace atomic absorption spectrometry can be used to vaporize the sample. Other devices including boats, ribbons, rods, and filaments, also can be used. The chosen device is heated in a series of steps to temperatures as high as 3000 K to produce a dry vapor and an aerosol, which are transported into the center of the plasma. A transient signal is produced due to matrix and element-dependent volatilization, so the detection system must be capable of time resolution better than 0.25 s. Concentration detection limits are typically 1-2 orders of magnitude better than those obtained via nebulization. Mass detection limits are typically in the range of tens of pg to ng, with a precision of 10% to 15%. 

Ozin et al. 107,108) performed matrix, optical experiments that resulted in the identification of the dimers of these first-row, transition metals. For Sc and Ti (4s 3d and 4s 3d, respectively), a facile dimerization process was observed in argon. It was found that, for Sc, the atomic absorptions were blue-shifted 500-1000 cm with respect to gas-phase data, whereas the extinction coefficients for both Sc and Scj were of the same order of magnitude, a feature also deduced for Ti and Ti2. The optical transitions and tentative assignments (based on EHMO calculations) are summarized in Table I. 

Cruz, R. B. and Loon, J. C. van "A Critical Study of the Application of Graphite-Furnace Non-Flame Atomic Absorption Spectrometry to the Determination of Trace Base Metals In Complex Heavy-Matrix Sample Solutions". Anal. Chlm. Acta (1974), 72, 231-243. 

W. Pennincks, P. Vankeerberghen, D.L. Massart and J. Smeyers-Verbeke, A knowledge-based computer system for the detection of matrix interferences. Atomic Absorption Spectrometric Methods, J. Anal. Atom. Spectrom. inch Atomic Absorption Spectrom. Updates, 10 (3) (1995) 207-214. 

Pauwels J, Hofmann C, Vandbcasteele C (1994) Calibration of solid sampling Zeeman atomic absorption spectrometry by extrapolation to zero matrix. Fresenius J Anal Chem 348 418-421. 

Note that the interfacing of LC techniques with MS puts significant constraints on the solvents that can be used i.e., they must be volatile, with a low salt concentration, for MS compatibility. Narrow-bore columns, which use much smaller amounts of salt and organic modifier, appear to have potential for facilitating IEC-MS applications.40 Despite the excellent sensitivity of MS detection for most elements, however, there are cases where matrix effects can interfere. In this situation, combination of IEC with atomic emission spectrometry (AES) or atomic absorption spectrometry (AAS) may be preferable, and can also provide better precision.21 32 4142 Other types of... 

Table 8.76 shows the main characteristics of voltammetry. Trace-element analysis by electrochemical methods is attractive due to the low limits of detection that can be achieved at relatively low cost. The advantage of using standard addition as a means of calibration and quantification is that matrix effects in the sample are taken into consideration. Analytical responses in voltammetry sometimes lack the predictability of techniques such as optical spectrometry, mostly because interactions at electrode/solution interfaces can be extremely complex. The role of the electrolyte and additional solutions in voltammetry are crucial. Many determinations are pH dependent, and the electrolyte can increase both the conductivity and selectivity of the solution. Voltammetry offers some advantages over atomic absorption. It allows the determination of an element under different oxidation states (e.g. Fe2+/Fe3+). 

Also in the literature, there is little discussion of the accuracy or reproducibility of the analytical technique used for determining the corresponding matrix and particle composition [37, 38], Various analytical methods that have been used to determine the particle concentration in the deposit include gravimetric analysis [29, 31, 39], x-ray fluorescence [5], atomic absorption spectroscopy [33, 40, 41-43], and micro-... 

A method has been developed for differentiating hexavalent from trivalent chromium [33]. The metal is electrodeposited with mercury on pyrolytic graphite-coated tubular furnaces in the temperature range 1000-3000 °C, using a flow-through assembly. Both the hexa- and trivalent forms are deposited as the metal at pH 4.7 and a potential at -1.8 V against the standard calomel electrode, while at pH 4.7, but at -0.3 V, the hexavalent form is selectively reduced to the trivalent form and accumulated by adsorption. This method was applied to the analysis of chromium species in samples of different salinity, in conjunction with atomic absorption spectrophotometry. The limit of detection was 0.05 xg/l chromium and relative standard deviation from replicate measurements of 0.4 xg chromium (VI) was 13%. Matrix interference was largely overcome in this procedure. 

As cadmium is one of the most sensitive graphite furnace atomic absorption determinations, it is not surprising that this is the method of choice for the determination of cadmium in seawater. Earlier workers separated cadmium from the seawater salt matrix prior to analysis. Chelation and extraction [ 121— 128], ion exchange [113,124,125,129], and electrodeposition [130,131] have all been studied. 

Lum and Callaghan [ 140 ] did not use matrix modification in the electother-mal atomic absorption spectrophotometric determination of cadmium in seawater. The undiluted seawater was analysed directly with the aid of Zeeman effect background correction. The limit of detection was 2 ng/1. 

Electrothermal atomic absorption spectrophotometry with Zeeman background correction was used by Zhang et al. [141] for the determination of cadmium in seawater. Citric acid was used as an organic matrix modifier and was found to be more effective than EDTA or ascorbic acid. The organic matrix modifier reduced the interferences from salts and other trace metals and gave a linear calibration curve for cadmium at concentrations < 1.6 pg/1. The method has a limit of detection of 0.019 pg/1 of cadmium and recoveries of 95-105% at the 0.2 pg of cadmium level. 

Han et al. [142] have reported an atomic absorption spectrometric method for the determination of cadmium in seawater using sodium phosphate for matrix modification. 

In order to overcome the problem of the high nonspecific absorption, alternative procedures have been tested, which involve prior separation of the trace metals from the salt matrix. Examples of extraction of trace metals from seawater as chelates with subsequent determination by electrothermal atomic absorption spectrometric procedures have been described [381,382], but these and similar methods are seldom effective and satisfactory when the matrix is very complex and the analyte concentration very low. 

Graphite-furnace atomic absorption spectrometry, although element-selective and highly sensitive, is currently unable to directly determine manganese at the lower end of their reported concentration ranges in open ocean waters. Techniques that have been successfully employed in recent environmental investigations have thus used a preliminary step to concentrate the analyte and separate it from the salt matrix prior to determination by atomic absorption spectrometry. 

Klinkhammer [432] has described a method for determining manganese in a seawater matrix at concentrations ranging from about 30 to 5500 ng/1. The samples are extracted with 4 nmol/1 8-hydroxyquinoline in chloroform, and the manganese in the organic phase is then back-extracted into 3 M nitric acid. The manganese concentrations are determined by graphite furnace atomic absorption spectrophotometry. The blank of the method is about 3.0 ng/1, and the precision from duplicate analyses is 9% (1 SD). 

The sensitivity achieved should enable seawater samples to be analysed for molybdenum, because the concentration of molybdenum in seawater is usually 2.1 -18.8 pg/1. The selected temperature of 1700-1850 °C during the charring stage permits separation of the seawater matrix from the analyte prior to atomisation with the Perkin-Elmer Model 603 atomic absorption spectrometer equipped with a heated graphite atomiser (HGA-2100). 

Graphite furnace atomic absorption spectrometry has also been used to determine zinc [610,611] in seawater with a detection limit of 2 ig [611]. Guevre-mont [610] has discussed the use of organic matrix modifiers for the direct determination of zinc. 

Tominaga et al. [682,683] studied the effect of ascorbic acid on the response of these metals in seawater obtained by graphite-furnace atomic absorption spectrometry from standpoint of variation of peak times and the sensitivity. Matrix interferences from seawater in the determination of lead, magnesium, vanadium, and molybdenum were suppressed by addition of 10% (w/v) ascorbic acid solution to the sample in the furnace. Matrix effects on the determination of cobalt and copper could not be removed in this way. These workers propose a direct method for the determination of lead, manganese, vanadium, and molybdenum in seawater. 

The application of palladium and magnesium nitrate matrix modifier for graphite furnace atomic absorption spectrometry has been discussed in detail [686]. The work has shown that a mixture of palladium and magnesium... 

Table 5.6 compares the ICP-AES results with data generated for the same sample by two other independent methods - isotope dilution spark source mass spectrometry (IDSSMS), and graphite furnace atomic absorption spectrometry (GFAAS). The IDSSMS method also uses 25-fold preconcentration of the metals and matrix separation using the ion exchange procedure, following isotope... 

In the analysis of seawater, isotope dilution mass spectrometry offers a more accurate and precise determination than is potentially available with other conventional techniques such as flameless AAS or ASV. Instead of using external standards measured in separate experiments, an internal standard, which is an isotopically enriched form of the same element, is added to the sample. Hence, only a ratio of the spike to the common element need be measured. The quantitative recovery necessary for the flameless atomic absorption and ASV techniques is not critical to the isotope dilution approach. This factor can become quite variable in the extraction of trace metals from the salt-laden matrix of seawater. Yield may be isotopically determined by the same experiment or by the addition of a second isotopic spike after the extraction has been completed. 

Interferences in atomic absorption measurements can arise from spectral, chemical and physical sources. Spectral interference resulting from the overlap of absorption lines is rare because of the simplicity of the absorption spectrum and the sharpness of the lines. However, broad band absorption by molecular species can lead to significant background interference. Correction for this may be made by matrix matching of samples and standards, or by use of a standard addition method (p. 30 et seq.). 

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