Atomic absorption spectrometry sources

Source Compiled from Parson, M. L. Major, S. Forster, A. R. Appl. Spectrosc. 1983,37, 411-418 Weltz, B. Atomic Absorption Spectrometry, VCH Deerfield Beach, FL, 1985. 

Inadequate regulation of atomizer temperature Is a major source of Imprecision In electrothermal atomic absorption spectrometry. The programmed heating of electrothermal atomizers can be achieved by five different methods, depending upon the electrical or physical parameters which are monltorled during... 

Aqueous standard solutions are a source of certain difficulties In electrothermal atomic absorption spectrometry of trace metals In biological fluids The viscosities and surface tensions of aqueous standard solutions are substantially less than the viscosities and surface tensions of serum, blood and other proteln-contalnlng fluids These factors Introduce volumetric disparities In pipetting of standard solutions and body fluids, and also cause differences In penetration of these liquids Into porous graphite tubes or rods Preliminary treatment of porous graphite with xylene may help to minimize the differences of liquid penetration (53,67) A more satisfactory solution of this problem Is preparation of standards In aqueous solutions of metal-free dextran (50-60 g/llter), as first proposed by Pekarek et al ( ) for the standardization of serum chromium analyses This practice has been used successfully by the present author for standardization of analyses of serum nickel The standard solutions which are prepared In aqueous dextran resemble serum In regard to viscosity and surface tension Introduction of dextran-contalnlng standard solutions Is an Important contribution to electrothermal atomic absorption analysis of trace metals In body fluids. 

Spectral overlap of emission and absorption wavelengths Is a potential cause of Interference In atomic absorption spectrometry (57) Thus, (a) the emission line of Fe at 352.424 nm Is close to the resonance line of N1 at 352.454, (b) the emission line of Sb at 217.023 nm Is close to the resonance line of Pb at 216.999 nm, and (c) the emission line of As at 228.812 nm Is close to the resonance line of Cd at 228.802 (57). To date, these practically coincident spectral lines have not been reported to be of practical Importance as sources of analytical Interference In atomic absorption analyses of biological materials. 

On the whole, the applications of plasma-source emission detection to GC in the field of polymer/additive analysis are limited. The same holds for GC-atomic absorption spectrometry [370]. 

Principles and Characteristics Plasma source techniques are more widely used in connection with liquid chromatography than atomic absorption spectrometry (see Section 7.3.3). ICP is a natural complement to liquid chromatography, and HPLC-ICP procedures... 

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... 

The measurement of very low levels of environmental pollutants is becoming increasingly important. The determination of lead, a cumulative toxin, is a good example. The current maximum allowable concentration of lead in British drinking water, before it enters the distribution network, is SO ng ml [29]. Although electrothermal atomization atomic-absorption spectrometry (AAS) can be used to measure this and lower concentrations, it is slow and requires considerable effort to ensure accurate results. Flames can provide simple and effective atom sources, but, if samples are aspirated directly, do not provide sufficient sensitivity. Thus, if a flame is to be used as the atom source, a preconcentration step is required. 

In the past, flames used for atomic absorption spectrometry have also been used for atomic emission spectrometry, and these are described in some detail in Chapter 2. However, the advent of plasma excitation sources has resulted in the demise of flame atomic emission spectrometry, for the reasons discussed in Section 4.2.3. 

The number of excited atoms at typical flame temperatures (ca 2200-3200 K) is very low indeed compared with the number of ground-state atoms, even for easily excited lines. For difficult-to-excite lines (e.g. Zn 213.9 nm), it can be shown that only about one excited atom will exist at any given time in an air-propane flame when aspirating a 1 mg 1 zinc solution. This is one reason why flames are poor sources for atomic emission spectrometry, but are well suited to atomic absorption spectrometry, i.e. most of the atoms are in the ground state. As will be seen, the typical temperatures obtainable in plasma sources are of the order of 8000 K, at which there is a much high ratio of excited-to ground-state atoms, and hence a much greater intensity of atomic emission. 

Describe the factors which cause broadening of spectral lines. In atomic absorption spectrometry, why is it preferable for the source line-width to be narrower than the absorption profile How can this be achieved What are the differing requirements for resolution in monochromators for atomic emission and for atomic absorption spectrometry ... 

Describe suitable instrumentation for sensitive analytical measurements in atomic absorption spectrometry. Include a discussion of the ways in which the atomic population in the atom cell may be maximized and why the light source is always a line source. 

Different analytical techniques such as ICP-OES (optical emission spectrometry with inductively coupled plasma source), XRF (X-ray fluorescence analysis), AAS (atomic absorption spectrometry) with graphite furnace and flame GF-AAS and FAAS, NAA (neutron activation analysis) and others, are employed for the trace analysis of environmental samples. The main features of selected atomic spectrometric techniques (ICP-MS, ICP-OES and AAS) are summarized in Table 9.20.1 The detection ranges and LODs of selected analytical techniques for trace analysis on environmental samples are summarized in Figure 9.15.1... 

Figure 21-19 Graphite furnace absorption spectrum of bronze dissolved in HN03. [From B. T. Jones. B. W Smith, and J. D. Winetordner. Continuum Source Atomic Absorption Spectrometry in a Graphite Furnace with Photodiode Array Detection. Anal. Chem. 1989,61. 1670.]...

In atomic absorption spectrometry (AA) the sample is vaporized and the element of interest atomized at high temperatures. The element concentration is determined based on the attenuation or absorption by the analyte atoms, of a characteristic wavelength emitted from a light source. The light source is typically a hollow cathode lamp containing the element to be measured. Separate lamps are needed for each element. The detector is usually a photomultiplier tube. A monochromator is used to separate the element line and the light source is modulated to reduce the amount of unwanted radiation reaching the detector. 

Atomic Fluorescence Spectrometry. A spectroscopic technique related to some of the types mentioned above is atomic fluorescence spectrometry (AFS). Like atomic absorption spectrometry (AAS), AFS requires a light source separate from that of the heated flame cell. This can be provided, as in AAS, by individual (or multielement lamps), or by a continuum source such as xenon arc or by suitable lasers or combination of lasers and dyes. The laser is still pretty much in its infancy but it is likely that future development will cause the laser, and consequently the many spectroscopic instruments to which it can be adapted to, to become increasingly popular. Complete freedom of wavelength selection still remains a problem. Unlike AAS the light source in AFS is not in direct line with the optical path, and therefore, the radiation emitted is a result of excitation by the lamp or laser source. 

Basic techniques for speciation analysis are typically composed of a succession of analytical steps, e.g. extraction either with organic solvents (e.g. toluene, dichloromethane) or different acids (e.g. acetic or hydrochloric acid), derivatisa-tion procedures (e.g. hydride generation, Grignard reactions), separation (gas chromatography (GC) or high-performance liquid chromatography (HPLC)), and detection by a wide variety of methods, e.g. atomic absorption spectrometry (AAS), mass spectrometry (MS), flame photometric detection (FPD), electron capture detection (ECD), etc. Each of these steps includes specific sources of error which have to be evaluated. 

High-Resolution Continuous Source Atomic Absorption Spectrometry... 

Welz, B., D.L. Borges, F.G. Lepri, M.G.R. Vale, and U. Heitmann. 2007. High-resolution continuum source electrothermal atomic absorption spectrometry—an analytical and diagnostic tool for trace analysis. Spectrochim. Acta B 62 873-883. 

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