Atomic fluorescence excitation sources

In many respects the selectivities of AFS when an atomic line excitation source is used and AAS should be similar, in so far as both depend upon overlap of extremely narrow absorption and emission line profiles. However, there are differences in the extent of interference effects, even for resonance fluorescence,... 

As indicated in Fig. 21.3, for both atomic absorption spectroscopy and atomic fluorescence spectroscopy a resonance line source is required, and the most important of these is the hollow cathode lamp which is shown diagrammatically in Fig. 21.8. For any given determination the hollow cathode lamp used has an emitting cathode of the same element as that being studied in the flame. The cathode is in the form of a cylinder, and the electrodes are enclosed in a borosilicate or quartz envelope which contains an inert gas (neon or argon) at a pressure of approximately 5 torr. The application of a high potential across the electrodes causes a discharge which creates ions of the noble gas. These ions are accelerated to the cathode and, on collision, excite the cathode element to emission. Multi-element lamps are available in which the cathodes are made from alloys, but in these lamps the resonance line intensities of individual elements are somewhat reduced. 

Both emission and absorption spectra are affected in a complex way by variations in atomisation temperature. The means of excitation contributes to the complexity of the spectra. Thermal excitation by flames (1500-3000 K) only results in a limited number of lines and simple spectra. Higher temperatures increase the total atom population of the flame, and thus the sensitivity. With certain elements, however, the increase in atom population is more than offset by the loss of atoms as a result of ionisation. Temperature also determines the relative number of excited and unexcited atoms in a source. The number of unexcited atoms in a typical flame exceeds the number of excited ones by a factor of 103 to 1010 or more. At higher temperatures (up to 10 000 K), in plasmas and electrical discharges, more complex spectra result, owing to the excitation to more and higher levels, and contributions of ionised species. On the other hand, atomic absorption and atomic fluorescence spectrometry, which require excitation by absorption of UV/VIS radiation, mainly involve resonance transitions, and result in very simple spectra. 

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. 

AFS quantifies the discrete radiation emitted by excited state atoms that have been excited by radiation from a spectral source. There are a number of mechanisms that are responsible for the atomic fluorescence signal resonance fluorescence, step-wise fluorescence, direct-line fluorescence, and sensitized fluorescence. Generally, the lowest resonance transition (l->0) is used for AFS. If a line source is used for excitation and if the atomic vapor is dilute, then the radiant power of the atomic... 

Figure 1.2 shows the basic instrumentation necessary for each technique. At this stage, we shall define the component where the atoms are produced and viewed as the atom cell. Much of what follows will explain what we mean by this term. In atomic emission spectroscopy, the atoms are excited in the atom cell also, but for atomic absorption and atomic fluorescence spectroscopy, an external light source is used to excite the ground-state atoms. In atomic absorption spectroscopy, the source is viewed directly and the attenuation of radiation measured. In atomic fluorescence spectroscopy, the source is not viewed directly, but the re-emittance of radiation is measured. 

In atomic fluorescence spectroscopy an intense excitation source is focused on to the atom cell. The atoms are excited then re-emit radiation, in all directions, when they return to the ground state. The radiation passes to a detector usually positioned at right-angles to the incident light. At low concentrations, the intensity of fluorescence is governed by the following relationship ... 

Electrothermal atomizers are also suitable for AFS as, when an inert gas atmosphere is used, quenching will be minimized. In the nuclear, electronic, semiconductor and biomedical industries where detection limits have to be pushed as low as 1 part in lO (or 0.1 pg g- in the original sample), electrothermal atomization with a laser as excitation source (LIF-ETA) may be used. Figure 6.5 shows schematically a common way of observing the fluorescence in LIF-ETA. The fluorescence signal can be efficiently collected by the combination of a plane mirror, with a hole at its centre to allow excitation by the laser, positioned at 45° with respect to the longitudinal axis of the tube and a lens chosen to focus the central part of the tube into the entrance slit of the fluorescence monochromator. 

Figure 21-1 Absorption, emission, and fluorescence by atoms in a flame. In atomic absorption, atoms absorb part of the light from the source and the remainder of the light reaches the detector. Atomic emission comes from atoms that are in an excited stale because of the high thermal energy of the flame. To observe atomic fluorescence, atoms are excited by an external lamp or laser. An excited atom can fall to a lower slate and emit radiation.

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. 

Fluorescence is spontaneous radiation that arises because of the stimulation of an atomic or molecular system to energies higher than equilibrium. This is illustrated in Figure 1 for a simple two-level atom. The atom is excited by absorption of a photon of energy hv. If the fluorescence is observed at 90° to a collimated excitation source, then a very small focal volume may be defined resulting in fine spatial resolution. The fluorescence power an optical system will collect is... 

If the flame background emission intensity is reduced considerably by use of an inert gas-sheathed (separated) flame, then an interference filter may be used rather than a monochromator, to give a non-dispersive atomic fluorescence spectrometer as illustrated in Figure 14.36-38 Noise levels are often further reduced by employing a solar blind photomultiplier as a detector of fluorescence emission at UV wavelengths. Such detectors do not respond to visible light. The excitation source is generally placed at 90° to the monochromator or detector. Surface-silvered or quartz mirrors and lenses are often used to increase the amount of fluorescence emission seen by the detector. 

The advent of tunable dye lasers has opened a new era in light sources for the excitation of atomic fluorescence. An increasing number of descriptions of these may be found in the literature [42], and populations of alkali atoms excited to their 2P resonance states, approaching the theoretical limit equilibrium of 50 %, have been reported [43]. 

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... 

Atomic fluorescence spectrometry (AFS) is the newest of the optical atomic spectroscopic methods. As in atomic absorption, an external source is used to excite the element of interest. Instead of measuring the attenuation of the source, however, the radiation emitted as a result of absorption is measured, often at right angles to avoid measuring the source radiation. 

Depending on the excitation method used, luminescence techniques are divided into photoluminescence excited by photons, cathodoluminescence generated under the action of cathode rays, X-ray luminescence excited by X-rays, candoluminescence generated under the action of heat, and sonoluminescence excited by ultrasound. Emission generated under the action of a stream of ions from alkali metals in vaccum is called ionoluminescence radiation which atoms emit on optical excitation in plasma is known as atomic fluorescence chemiluminescence is the emission of radiation generated by the energy of chemical reactions, it does not require an external excitation source. The excitation source needed in each particular case is chosen on the basis of this classification. 

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