Laser-excited flame atomic fluorescence

Laser Fluorescence Noise Sources. Finally, let us examine a technique with very complex noise characteristics, laser excited flame atomic fluorescence spectrometry (LEAFS). In this technique, not only are we dealing with a radiation source as well as an atomic vapor cell, as In atomic absorption, but the source Is pulsed with pulse widths of nanoseconds to microseconds, so that we must deal with very large Incident source photon fluxes which may result in optical saturation, and very small average signals from the atomic vapor cell at the detection limit [22]. Detection schemes involve gated amplifiers, which are synchronized to the laser pulse incident on the flame and which average the analyte fluorescence pulses [23]. 

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.

Figure 21-1 also illustrates an atomic fluorescence experiment. Atoms in the flame are irradiated by a laser to promote them to an excited electronic state from which they can fluoresce to return to the ground state. Figure 21-4 shows atomic fluorescence from 2 ppb of lead in tap water. Atomic fluorescence is potentially a thousand times more sensitive than atomic absorption, but equipment for atomic fluorescence is not common. An important example of atomic fluorescence is in the analysis of mercury (Box 21-1). 

The laser atomic fluorescence excitation and emission spectra of sodium in an air-acetylene flame are shown below. In the excitation spectrum, the laser (bandwidth = 0.03 nm) was scanned through various wavelengths while the detector monochromator (bandwidth = 1.6 nm) was held fixed near 589 nm. In the emission spectrum, the laser was fixed at 589.0 nm, and the detector monochromator wavelength was varied. Explain why the emission spectrum gives one broad band, whereas the excitation spectrum gives two sharp lines. How can the excitation linewidths be much narrower than the detector monochromator bandwidth ... 

Fluorescence excitation and emission spectra of the two sodium D lines in an air-acetylene flame, (a) In the excitation spectrum, the laser was scanned, (to) In the emission spectrum, the monochromator was scanned. The monochromator slit width was the same for both spectra. [From s. J. Weeks, H. Haraguchl, and J. D. Wlnefordner, Improvement of Detection Limits in Laser-Excited Atomic Fluorescence Flame Spectrometry," Anal. Chem. 1976t 50,360.]... 

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. 

Walton et al. [269] separated organomanganese and organotin compounds by high performance liquid chromatography using laser excited atomic fluorescence in a flame as a high sensitivity detector. 

Gaussian Laser Profile-Voigt Atom Profile. This case turns out to be a better approximation of our experimental situation, i.e., the laser FWHM is fairly broad compared to the absorption line width and the absorption profile of atoms in an atmospheric combustion flame is described by a Voigt profile. Here the laser is assumed to have a Gaussian spectral profile as well as a Gaussian atomic absorption profile. In this case, convolution of two Gaussian functions is still a Gaussian function. Evaluation of the ratio n2/nT, and the fluorescence radiance. Bp, allows determination of the half width of the fluorescence excitation profile, 6X... 

Method 2. Saturation Method for Sequential Pumping. In this method, atomic fluorescence of the inorganic probe is produced at 3+1 and at 3+2 after excitation at 1+3 and/or 2+3 respectively. However, in this case, it is necessary to "saturate" the excited level, 3, in order to use the methodic In addition, in order for the flame temperature to be evaluated it is necessary for the mixing first order rate constant, k2i, between the metastable, 2, and ground state, 1, to be much greater (> 20X) than the sum of the total deactivation rate constants between levels 3 and 1 and also between 3 and 2. This method also requires calibration of the spectrometric measurement system, saturation of level 3, corrections or minimization of scatter and post filter effects, and beam matching of 2 dye laser beams are needed for the excitation process. 

F9. Fraser, L. M., and Winefordner, J. D., Laser-excited atomic fluorescence flame spectrometry. Anal. Chem. 43, 1693-1696 (1971). 

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... 

In flame AFS, elements which form thermally stable oxides such as Al, Mg, Nb, Ta, Zr and the rare earths are hampered by insufficient atomization. This is not the case when an ICP is used as the fluorescence volume. Here the detection limits for laser excitation and non-resonant fluorescence are lower than in ICP-AES (Table 18) [663]. ICP-AFS can be performed for both atomic and ionic states [664]. 

The application of microtron photon activation analysis with radiochemical separation in environmental and biological samples was described by Randa et al. (2001), and both flame and plasma emission spectroscopic methods are also widely used. A more recently developed technique is that of laser-excited atomic fluorescence spectrometry (LEAFS) (Cheam et al. 1998). 

The excitation source can be a continuum or a line-like radiation source. Research on atomic fluorescence spectrometry has been connected with the examination of intense radiation sources such as electrodeless discharge lamps and lasers. Various flames, plasmas, and furnaces have been employed as atomizing devices. 

Butcher DJ, Dougherty JP, Preli FR, et al. (1988) Laser excited atomic fluorescence spectrometry in flames, plasmas and electrothermal atomizers. Journal of Analytical Spectrometry 3 1059-1078. 

In atomic fluorescence spectrometry (AFS), the analyte is introduced into an atomizer (flame, plasma, glow discharge, furnace) and excited by monochromatic radiation emitted by a primary source. The latter can be a continuous source (xenon lamp) or a line source (hollow cathode lamp, electrodeless discharge lamp, or tuned laser). Subsequently, the fluorescence radiation, which may be of the same wavelength (resonance fluorescence) or of longer wavelength (nonresonance fluorescence), is measured. 

M. Alden, P. Grafstrdm, H. Lundberg, S. Svanberg Spatially resolved temperature measurements in a flame using laser-excited two-line atomic fluorescence and diode-array detection. Opt. Lett. 8, 241 (1983)... 

Possible applications of laser enhanced ionization in flame diagnostics are 1. simultaneous observation of ionization and fluorescence signals from various levels might provide more information on the sequence of processes leading to and from the ionization continuum 2. the measurement of ion mobilities, relating to cross-sections for elastic collisions between ions and flame particles 3. measurement of ionization rate constants relating to cross-sections for inelastic collisions between excited atoms and other flame particles 4. measurement of recombination rate constants, relating to cross-sections for inelastic collisions between ions, electrons and neutrals. 

Chemiluminescence and photoluminescence in diatomic iron oxide, Rb2, and alkali-metal dimers with halogen atoms and metal vapour-oxidant flames,202 203 lifetime measurements of selectively excited states of diatomic hydrides,204 photodissociation of alkali-metal halide vapours,206 spin-orbit relaxation of the HTe ( 2IIi) radical,20 the photodecomposition of metal carbonyl anions such as [Mn(C04)] in the vapour phase,207 and the fluorescence of Rhodamine 6G in the vapour phase 208 have been studied in recent reports. In the last study it was concluded that an insufficient concentration of the fluorescing dye could be maintained in the vapour phase to permit laser action to occur. 

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