Electrothermal techniques

The methods already described have illustrated the wide applicability of flame atomisation techniques to the analysis of non-ferrous alloys. The introduction of electrothermal atomisation has enabled the direct determination of sub-part per million levels of impurities. The presence of very low levels of lead, bismuth and other low melting point metals is known to have a deleterious effect on the metallurgical properties of nickel alloys. 

Welcher et al. [ 10] have described the direct determination of trace quantities of lead, bismuth, selenium, tellurium and thallium in high-temperature nickel alloys using electrothermal atomisation. 

INSTRUMENTAL PARAMETERS FOR THE ANALYSIS OF NICKEL-BASED ALLOYS 

Chromium 520.8 nitrous oxide/ acetylene Chromium is subject to interference from nickel. It is advisable to adjust the fuel flow until the absorbance obtained from a 1500 Mg ml-1 chromium solution and a 1500 Mg ml-1 chromium plus nickel at the sample level produce the same absorbance 

Bismuth 223.1 air/acetylene Sample preparation. Dissolve 2.000 g of sample in 12 ml of hydrochloric acid, 6 ml of nitric acid and 20 ml of water in a PTFE beaker. Evaporate the solution to 10- 12 ml, cool, add 1 ml of hydrofluoric acid dropwise and boil for five minutes. Cool, add 5 ml of 1% boric acid solution and dilute to 50 ml. Background correction using a UV continuum source is advisable for bismuth 

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Electrothermal techniques are very sensitive, as already noted. For example, a 10 ppm lead standard produces an absorption signal of about... 

Flame and electrothermal techniques Both atomic absorption and emission have been used, with the former most widely applied to the analysis of minor soil components. Detection limits can often be very similar to the concentration found in extraction solutions of natural soils. While the sampling procedure is easily automated, AAS, it is inefficient (both time and sample volume) for routine multielement... 

Inductively coupled argon plasma (icp) and direct current argon plasma (dcp) atomic emission spectrometry are solution techniques that have been appHed to copper-beryUium, nickel—beryUium, and aluminum—beryUium aUoys, beryUium compounds, and process solutions. The internal reference method, essential in spark source emission spectrometry, is also useful in minimizing drift in plasma emission spectrometry (17). Electrothermal (graphite... 

The scope of this review Is limited to electrothermal atomic absorption spectrometry, with emphasis upon Its clinical applications. This article Is Intended to supplement the recent treatises on the basic technique which have been written by Aggett and Sprott ( ) > Ingle ( ), Klrkbrlght (34), Price (63), and Woodrlff (83). This resume does not consider various related topics, such as (a) atomic fluorescence or emission spectrometry (b) non-flame atomization devices which employ direct current... 

Plasmas compare favourably with both the chemical combustion flame and the electrothermal atomiser with respect to the efficiency of the excitation of elements. The higher temperatures obtained in the plasma result in increased sensitivity, and a large number of elements can be efficiently determined. Common plasma sources are essentially He MIP, Ar MIP and Ar ICP. Helium has a much higher ionisation potential than argon (24.5 eV vs. 15.8 eV), and thus is a more efficient ionisation source for many nonmetals, thereby resulting in improved sensitivity. Both ICPs and He MIPs are utilised as emission detectors for GC. Plasma-source mass spectrometry offers selective detection with excellent sensitivity. When coupled to chromatographic techniques such as GC, SFC or HPLC, it provides a method for elemental speciation. Plasma-source detection in GC is dominated by GC-MIP-AES... 

Principles and Characteristics Flame emission instruments are similar to flame absorption instruments, except that the flame is the excitation source. Many modem instruments are adaptable for either emission or absorption measurements. Graphite furnaces are in use as excitation sources for AES, giving rise to a technique called electrothermal atomisation atomic emission spectrometry (ETA AES) or graphite furnace atomic emission spectrometry (GFAES). In flame emission spectrometry, the same kind of interferences are encountered as in atomic absorption methods. As flame emission spectra are simple, interferences between overlapping lines occur only occasionally. 

The concept of selectivity and specificity has been applied to characterize interferences appearing in two different ICP-MS techniques (Horn [2000]). Classical ICP-MS with pneumatic nebulization and ETV-ICP-MS are compared for the determination of traces of zinc in sea-water. Whereas spectral interferences decrease using the ETV device, nonspectral interferences increase significantly (Bjorn et al. [1998]). A quantitative comparison of the both analytical procedures, here called PN (pneumatic nebulization) and ETV (electrothermal vaporization, Sturgeon and Lam [1999]) is possible by means the specificity as a function of the Zn concentration (Horn [2000]). The spectral interferences on the four zinc isotopes are listed in Table 7.4. 

Cimadevilla et al. [691] compared wall, platform, and graphite furnace probe atomisation techniques in electrothermal atomic absorption spectrometry for the determination of ig/l levels of silver, cadmium, and lead in seawater. 

Bruland et al. [122] have shown that seawater samples collected by a variety of clean sampling techniques yielded consistent results for copper, cadmium, zinc, and nickel, which implies that representative uncontaminated samples were obtained. A dithiocarbamate extraction method coupled with atomic absorption spectrometry and flameless graphite furnace electrothermal atomisation is described which is essentially 100% quantitative for each of the four metals studied, has lower blanks and detection Emits, and yields better precision than previously published techniques. A more precise and accurate determination of these metals in seawater at their natural ng/1 concentration levels is therefore possible. Samples analysed by this procedure and by concentration on Chelex 100 showed similar results for cadmium and zinc. Both copper and nickel appeared to be inefficiently removed from seawater by Chelex 100. Comparison of the organic extraction results with other pertinent investigations showed excellent agreement. 

Chappie and Byrne [743] applied an electrothermal vaporisation inductively coupled plasma technique to the determination of copper, cobalt, manganese, nickel, and vanadium in seawater in amounts down to 3-140 ppt. 

Batley [780] found that in situ deposition of lead and cadmium on a mercury-coated tube was the more versatile technique. The mercury film, deposited in the laboratory, is stable on the dried tubes which are used later for field electrodeposition. The deposited metals were then determined by electrothermal AAS. 

Batley [28] examined the techniques available for the in situ electrodeposition of lead and cadmium in estuary water. These included anodic stripping voltammetry at a glass carbon thin film electrode and the hanging drop mercury electrode in the presence of oxygen and in situ electrodeposition on mercury coated graphite tubes. Batley [28] found that in situ deposition of lead and cadmium on a mercury coated tube was the more versatile technique. The mercury film, deposited in the laboratory, is stable on the dried tubes which are used later for field electrodeposition. The deposited metals were then determined by electrothermal atomic absorption spectrometry, Hasle and Abdullah [29] used differential pulse anodic stripping voltammetry in speciation studies on dissolved copper, lead, and cadmium in coastal sea water. 

Electrothermic process, for zinc, 26 577 Electrothermic zinc smelting, 26 612 Electrotransport technique, for purifying vanadium, 25 522... 

Nonflame atom reservoirs have been developed for specific atomic spectrometric techniques. Electrothermal atomizers (carbon rods, carbon furnaces, or tantalum ribbons) have been developed for AAS or AFS since they require the generation of ground state atoms, whereas... 

Conventional flame techniques present problems when dealing with either small or solid samples and in order to overcome these problems the electrothermal atomization technique was developed. Electrothermal, or flameless, atomizers are electrically heated devices which produce an atomic vapour (Figure 2.36). One type of cuvette consists of a graphite tube which has a small injection port drilled in the top surface. The tube is held between electrodes, which supply the current for heating and are also water-cooled to return the tube rapidly to an ambient temperature after atomization. 

Although electrothermal atomizers have certain advantages, they are slower than flame techniques particularly when large numbers of samples have to be analysed, and the transient readings which result from such methods may show poorer precision than do the steady readings obtained by sample aspiration. 

Although electrothermal vaporization has been widely accepted as an extension of atomic absorption, its use in inductively coupled plasma spectroscopy is fairly recent. In this technique the requirement for the vaporizer is somewhat different—the electrothermal vaporizer does not have to double as the atom cell. In fact, it is only needed to effect efficient and reproducible sample transfer from the rod, or a similar device, into the plasma. 

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