Atomic fluorescence detection limits

Some Experimental Detection Limits and Wavelengths of Detection in Atomic Fluorescence Spectroscopy"... 

The choice between X-ray fluorescence and the two other methods will be guided by the concentration levels and by the duration of the analytical procedure X-ray fluorescence is usually less sensitive than atomic absorption, but, at least for petroleum products, it requires less preparation after obtaining the calibration curve. Table 2.4 shows the detectable limits and accuracies of the three methods given above for the most commonly analyzed metals in petroleum products. For atomic absorption and plasma, the figures are given for analysis in an organic medium without mineralization. 

The detection limits in the table correspond generally to the concentration of an element required to give a net signal equal to three times the standard deviation of the noise (background) in accordance with lUPAC recommendations. Detection limits can be confusing when steady-state techniques such as flame atomic emission or absorption, and plasma atomic emission or fluorescence, which... 

The section on Spectroscopy has been retained but with some revisions and expansion. The section includes ultraviolet-visible spectroscopy, fluorescence, infrared and Raman spectroscopy, and X-ray spectrometry. Detection limits are listed for the elements when using flame emission, flame atomic absorption, electrothermal atomic absorption, argon induction coupled plasma, and flame atomic fluorescence. Nuclear magnetic resonance embraces tables for the nuclear properties of the elements, proton chemical shifts and coupling constants, and similar material for carbon-13, boron-11, nitrogen-15, fluorine-19, silicon-19, and phosphoms-31. 

Highly sensitive iastmmental techniques, such as x-ray fluorescence, atomic absorption spectrometry, and iaductively coupled plasma optical emission spectrometry, have wide appHcation for the analysis of silver ia a multitude of materials. In order to minimize the effects of various matrices ia which silver may exist, samples are treated with perchloric or nitric acid. Direct-aspiration atomic absorption (25) and iaductively coupled plasma (26) have silver detection limits of 10 and 7 l-lg/L, respectively. The use of a graphic furnace ia an atomic absorption spectrograph lowers the silver detection limit to 0.2 l-ig/L. 

As atomic fluorescence spectrometer a mercury analyzer Mercur , (Analytik-Jena, Germany) was used. In the amalgamation mode an increase of sensitivity by a factor of approximately 7-8 is obtained compared with direct introduction, resulting in a detection limit of 0,09 ng/1. This detection limit has been improved further by pre-concentration of larger volumes of samples and optimization of instrumental parameters. Detection limit 0,02 ng/1 was achieved, RSD = 1-6 %. 

The complex of the following destmctive and nondestmctive analytical methods was used for studying the composition of sponges inductively coupled plasma mass-spectrometry (ICP-MS), X-ray fluorescence (XRF), electron probe microanalysis (EPMA), and atomic absorption spectrometry (AAS). Techniques of sample preparation were developed for each method and their metrological characteristics were defined. Relative standard deviations for all the elements did not exceed 0.25 within detection limit. The accuracy of techniques elaborated was checked with the method of additions and control methods of analysis. 

Raman spectroscopy has enjoyed a dramatic improvement during the last few years the interference by fluorescence of impurities is virtually eliminated. Up-to-date near-infrared Raman spectrometers now meet most demands for a modern analytical instrument concerning applicability, analytical information and convenience. In spite of its potential abilities, Raman spectroscopy has until recently not been extensively used for real-life polymer/additive-related problem solving, but does hold promise. Resonance Raman spectroscopy exhibits very high selectivity. Further improvements in spectropho-tometric measurement detection limits are also closely related to advances in laser technology. Apart from Raman spectroscopy, areas in which the laser is proving indispensable include molecular and fluorescence spectroscopy. The major use of lasers in analytical atomic... 

Winefordner JD, Parsons ML, Mansfield JM, McCarthy WJ (1967) Derivation of expressions for calculation of limiting detectable atomic concentration in atomic fluorescence flame spectrometry. Anal Chem 39 436... 

The instrumentation required for atomic fluorescence measurements is simpler than that used for absorption. As the detector is placed so as to avoid receiving radiation directly from the lamp, it is not strictly necessary to use a sharp-line source or a monochromator. Furthermore, fluorescence intensities are directly related to the intensity of the primary radiation so that detection limits can be improved by employing a high-intensity discharge lamp. 

In principle, atomic fluorescence is a simpler and more versatile technique than atomic absorption, but suffers from a susceptibility to quenching effects and to background noise arising from the scattering of radiation by particles in the flame. The latter is particularly serious for refractory materials and in high-temperature flames. Detection limits for some elements are lower than by atomic absorption or flame emission measurements, e.g. elements with resonance lines around 200 nm or below, such as As, Se,... 

Te. Instruments based upon the use of a chemical flame as the atom reservoir have not proved to be generally successful. The introduction of the ICP torch renewed interest in atomic fluorescence and new instruments based on the ICP torch as a source of free atoms were constructed. However, these seem to have been only slightly more satisfactory than earlier instruments and have not come into widespread use. Some detection limits are included in Table 8.6. 

Table 8.6 Some detection limits for atomic absorption, fluorescence and flame emission methods...

Various workers have discussed the application of atomic absorption spectrometry to the determination of selenium in rocks [159,160] achieving detection limits of 0.06g g-1 [159] and 1.4xl0 10g g-1 [160] respectively. Hydride generation and measurement of hydride fluorescence has been used to determine selenium [120, 161] with a sensitivity of 0.06ug Se mL 1 which is 5-30 times than is achieved by conventional atomic absorption spectrometry. 

Manganese in aqueous solution may be analyzed by several instrumental techniques including flame and furnace AA, ICP, ICP-MS, x-ray fluorescence and neutron activation. For atomic absorption and emission spectrometric determination the measurement may be done at the wavelengths 279.5, 257.61 or 294.92 nm respectively. The metal or its insoluble compounds must be digested with nitric acid alone or in combination with another acid. Soluble salts may be dissolved in water and the aqueous solution analyzed. X-ray methods may be applied for non-destructive determination of the metal. The detection limits in these methods are higher than those obtained by the AA or ICP methods. ICP-MS is the most sensitive technique. Several colorimetric methods also are known, but such measurements require that the manganese salts be aqueous. These methods are susceptible to interference. 

With analytical methods such as x-ray fluorescence (XRF), proton-induced x-ray emission (PIXE), and instrumental neutron activation analysis (INAA), many metals can be simultaneously analyzed without destroying the sample matrix. Of these, XRF and PEXE have good sensitivity and are frequently used to analyze nickel in environmental samples containing low levels of nickel such as rain, snow, and air (Hansson et al. 1988 Landsberger et al. 1983 Schroeder et al. 1987 Wiersema et al. 1984). The Texas Air Control Board, which uses XRF in its network of air monitors, reported a mean minimum detectable value of 6 ng nickel/m (Wiersema et al. 1984). A detection limit of 30 ng/L was obtained using PIXE with a nonselective preconcentration step (Hansson et al. 1988). In these techniques, the sample (e.g., air particulates collected on a filter) is irradiated with a source of x-ray photons or protons. The excited atoms emit their own characteristic energy spectrum, which is detected with an x-ray detector and multichannel analyzer. INAA and neutron activation analysis (NAA) with prior nickel separation and concentration have poor sensitivity and are rarely used (Schroeder et al. 1987 Stoeppler 1984). 

Elements such as As, Se and Te can be determined by AFS with hydride sample introduction into a flame or heated cell followed by atomization of the hydride. Mercury has been determined by cold-vapour AFS. A non-dispersive system for the determination of Hg in liquid and gas samples using AFS has been developed commercially (Fig. 6.4). Mercury ions in an aqueous solution are reduced to mercury using tin(II) chloride solution. The mercury vapour is continuously swept out of the solution by a carrier gas and fed to the fluorescence detector, where the fluorescence radiation is measured at 253.7 nm after excitation of the mercury vapour with a high-intensity mercury lamp (detection limit 0.9 ng I l). Gaseous mercury in gas samples (e.g. air) can be measured directly or after preconcentration on an absorber consisting of, for example, gold-coated sand. By heating the absorber, mercury is desorbed and transferred to the fluorescence detector. 

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. 

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.]... 

In experiments where a higher degree of sensitivity and selectivity is required, fluorescence and mass-selective detectors have been applied. Picomole limits of detection offered by fluorescence makes it ideal for routine analysis requiring high sensitivity. Mass spectrometry has also proven to be both a sensitive and efficient way to identify numerous chlorophyll derivatives (unitf4.s). van Breemen et al. (1991) utilized both fast atom bombardment (FAB) and tandem mass spectrometry (MS/MS) for the structural characterization and mass determination of numerous deriva-... 

Thomas and Sniatecki [51] also performed an analysis of trace amounts of arsenic species in natural waters using hydride generation IPC-ICP-MS. Six arsenic species were determined with detection limits in the range 1.0-3.0 fig l-1 and total arsenic was determined using hydride generation by atomic fluorescence detection. It was found that the predominant species present in bottled mineral water samples was always As(V) with very low levels of As(III). The authors described how the system required . .. further work using special chromatographic software. .. to improve the quantitative measurement at a natural level. ... 

A number of analytical methods were developed for determination of elemental mercury. The methods are reviewed in Refs. [1-4]. They include traditional analytical techniques, such as atomic adsorption spectroscopy (AAS), atomic fluorescence spectroscopy (AFS), and atomic emission spectroscopy (AES). The AAS is based on measurements of optical adsorption at 253.7 or 184.9 nm. Typical value of the detection limit without pre-concentration step is over 1 pg/l. The AEF is much more sensitive and allows one to detect less than 0.1ng/l of mercury... 

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