Spark excitation techniques

Many analytical applications of atomic spectroscopy produce their spectra by arc or spark excitation techniques and these methods form the basis for much of the present practice in the field. The historical development in this area is most difficult to document since almost from the start, after observations of the spectrum from the sun, the attempt was to utilize high-energy sources. This led immediately to arc and spark methods. The present-day applications of the arc or spark are improvements of the early work with attempts to better stabilize and control excitation conditions within the arc or spark in an effort to improve analytical data derived from the spectra. These techniques will be discussed in Chapter 5, which deals with accessory equipment for arc and spark spectrochemical analysis. 

Besides plasmas, which are at the forefront of thermal atomisation devices, other excitation processes can be used. These methods rely on sparks or electrical arcs. They are less sensitive and take longer to use than methods that operate with samples in solution. These excitation techniques, with low throughputs, are mostly used in semi-quantitative analysis in industry (Fig. 15.2). Compared to the plasma torch, thermal homogeneity in these techniques is more difficult to master. 

There are different techniques in atomic emission spectroscopy that are based upon the types of excitation and detection used. Under this heading arc and spark excitation and photographic and multiphotometric detection will be discussed. Flame photometry although by principle belonging to this group will be discussed together with atomic absorption spectrometry. 

The early use of a flame as an excitation source for analytical emission spectroscopy dates back to HerscheF and Talbot, who identified alkali metals by flame excitation. The work of Kirchhoff and Bunsen also was basic to the establishment of this technique of atomic excitation. One of the earliest uses of flame excitation was for the determination of sodium in plant ash (1873) by Champion, Pellet, and Grenier.Thus use of the flame paralleled that of arc and spark excitation in the 1800 s. 

The predorninant method for the analysis of alurninum-base alloys is spark source emission spectroscopy. SoHd metal samples are sparked direcdy, simultaneously eroding the metal surface, vaporizing the metal, and exciting the atomic vapor to emit light ia proportion to the amount of material present. Standard spark emission analytical techniques are described in ASTM ElOl, E607, E1251 and E716 (36). A wide variety of weU-characterized soHd reference materials are available from major aluminum producers for instmment caUbration. 

The basic instrumentation used for spectrometric measurements has already been described in the previous chapter (p. 277). Methods of excitation, monochromators and detectors used in atomic emission and absorption techniques are included in Table 8.1. Sources of radiation physically separated from the sample are required for atomic absorption, atomic fluorescence and X-ray fluorescence spectrometry (cf. molecular absorption spectrometry), whereas in flame photometry, arc/spark and plasma emission techniques, the sample is excited directly by thermal means. Diffraction gratings or prism monochromators are used for dispersion in all the techniques including X-ray fluorescence where a single crystal of appropriate lattice dimensions acts as a grating. Atomic fluorescence spectra are sufficiently simple to allow the use of an interference filter in many instances. Photomultiplier detectors are used in every technique except X-ray fluorescence where proportional counting or scintillation devices are employed. Photographic recording of a complete spectrum facilitates qualitative analysis by optical emission spectrometry, but is now rarely used. 

A technique that utilizes a solid sample for light emission is spark emission spectroscopy. In this technique, a high voltage is used to excite a solid sample held in an electrode cup in such a way that when a spark is created with a nearby electrode, atomization, excitation, and emission occur and the emitted light is measured. Detection of what lines are emitted allows for qualitative analysis of the solid material. Detection of the intensity of the lines allows for quantitative analysis. 

Finally, direct solid analysis by optical and mass spectrometry will be presented in Section 1.5. This alternative is becoming more appealing nowadays and implemented in laboratories because of the many advantages brought about by eliminating the need to dissolve the sample. Techniques based on the use of atomiser/excitation/ionisation sources such as sparks, lasers and glow discharges will be briefly described in that section. 

This emission of light from elements was reported as early as the mid-1700s and was later the basis of discovering four elements by Kirchoff and Bunsen in the mid-1800s. However, it was not until the 20th century that the technique really became a useful analytical tool. The first analytical instruments used a spark discharge to provide the energy to excite the atoms so that... 

Whatever the analytical method and the determinand may be, the greatest care should be devoted to the proper selection and use of internal standards, careful preparation of blanks and adequate calibration to avoid serious mistakes. Today the Antarctic investigator has access to a multitude of analytical techniques, the scope, detection power and robustness of which were simply unthinkable only two decades ago. For chemical elements they encompass Atomic Absorption Spectrometry (AAS) [with Flame (F) and Electrothermal Atomization (ETA) and Hydride or Cold Vapor (HG or CV) generation]. Atomic Emission Spectrometry (AES) [with Inductively Coupled Plasma (ICP), Spark (S), Flame (F) and Glow Discharge/Hollow Cathode (HC/GD) emission sources], Atomic Fluorescence Spectrometry (AFS) [with HC/GD, Electrodeless Discharge (ED) and Laser Excitation (LE) sources and with the possibility of resorting to the important Isotope... 

Not only is there a need for the characterization of raw bulk materials but also the requirement for process controled industrial production introduced new demands. This was particularly the case in the metals industry, where production of steel became dependent on the speed with which the composition of the molten steel during converter processes could be controlled. After World War 11 this task was efficiently dealt with by atomic spectrometry, where the development and knowledge gained about suitable electrical discharges for this task fostered the growth of atomic spectrometry. Indeed, arcs and sparks were soon shown to be of use for analyte ablation and excitation of solid materials. The arc thus became a standard tool for the semi-quantitative analysis of powdered samples whereas spark emission spectrometry became a decisive technique for the direct analysis of metal samples. Other reduced pressure discharges, as known from atomic physics, had been shown to be powerful radiation sources and the same developments could be observed as reliable laser sources become available. Both were found to offer special advantages particularly for materials characterization. 

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