Flame Emission Interferences

Choice of Atomization and Excitation Source Except for the alkali metals, detection limits when using an ICP are significantly better than those obtained with flame emission (Table 10.14). Plasmas also are subject to fewer spectral and chemical interferences. For these reasons a plasma emission source is usually the better choice. 

Minimizing Spectral Interferences The most important spectral interference is a continuous source of background emission from the flame or plasma and emission bands from molecular species. This background emission is particularly severe for flames in which the temperature is insufficient to break down refractory compounds, such as oxides and hydroxides. Background corrections for flame emission are made by scanning over the emission line and drawing a baseline (Figure 10.51). Because the temperature of a plasma is... 

Accuracy When spectral and chemical interferences are insignificant, atomic emission is capable of producing quantitative results with accuracies of 1-5%. Accuracy in flame emission frequently is limited by chemical interferences. Because the higher temperature of a plasma source gives rise to more emission lines, accuracy when using plasma emission often is limited by stray radiation from overlapping emission lines. 

In a simple flame (emission) photometer an interference filter (Section 17.7) can be used. In more sophisticated flame emission spectrophotometers which require better isolation of the emitted frequency, a prism or a grating monochromator is employed. 

Various factors may affect the flame emission of a given element and lead to interference with the determination of the concentration of a given element. 

With flame emission spectroscopy, there is greater likelihood of spectral interferences when the line emission of the element to be determined and those due to interfering substances are of similar wavelength, than with atomic absorption spectroscopy. Obviously some of such interferences may be eliminated by improved resolution of the instrument, e.g. by use of a prism rather than a filter, but in certain cases it may be necessary to select other, non-interfering, lines for the determination. In some cases it may even be necessary to separate the element to be determined from interfering elements by a separation process such as ion exchange or solvent extraction (see Chapters 6, 7). 

Flame emission spectroscopy - continued evaluation methods, 800 flames, temperature of, 784 general discussion, 779 interferences, 791 chemical, 792 spectral, 792... 

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. 

McCracken et al. 164) compared atomic absorption with the tetraphenyl-boron method for determining potassium in 1190 fertilizers, and very close agreement was found between the two methods. Hoover and Reagor 16S) also found good agreement between the two methods, and atomic absorption was far more rapid. They reported that the 7665 A potassium line was more subject to interference than the less sensitive 4044 A line. Temperli and Misteli 166> reported far better results for low concentrations of potassium in soil extracts by atomic absorption spectroscopy than by flame emission spectroscopy. 

Table 8.7). Thus, intensity and concentration are directly proportional. However, the intensity of a spectral line is very sensitive to changes in flame temperature because such changes can have a pronounced effect on the small proportion of atoms occupying excited levels compared to those in the ground state (p. 274). Quantitative measurements are made by reference to a previously prepared calibration curve or by the method of standard addition. In either case, the conditions for measurement must be carefully optimized with reference to the choice of emission line, flame temperature, concentration range of samples and linearity of response. Relative precision is of the order of 1-4%. Flame emission measurements are susceptible to interferences from numerous sources which may enhance or depress line intensities. 

Flame emission spectrometry is used extensively for the determination of trace metals in solution and in particular the alkali and alkaline earth metals. The most notable applications are the determinations of Na, K, Ca and Mg in body fluids and other biological samples for clinical diagnosis. Simple filter instruments generally provide adequate resolution for this type of analysis. The same elements, together with B, Fe, Cu and Mn, are important constituents of soils and fertilizers and the technique is therefore also useful for the analysis of agricultural materials. Although many other trace metals can be determined in a variety of matrices, there has been a preference for the use of atomic absorption spectrometry because variations in flame temperature are much less critical and spectral interference is negligible. Detection limits for flame emission techniques are comparable to those for atomic absorption, i.e. from < 0.01 to 10 ppm (Table 8.6). Flame emission spectrometry complements atomic absorption spectrometry because it operates most effectively for elements which are easily ionized, whilst atomic absorption methods demand a minimum of ionization (Table 8.7). 

The procedure is strictly analogous to that used for absorbance measurements in UV and visible molecular spectrometry (p. 355). To avoid interference from emission by excited atoms in the flame and from random background emission by the flame, the output of the lamp is modulated, usually at 50 Hz, and the detection system tuned to the same frequency. Alternatively, a mechanical chopper which physically interrupts the radiation beam, can be used to simulate modulation of the lamp output. 

Atomic absorption spectrometry is one of the most widely used techniques for the determination of metals at trace levels in solution. Its popularity as compared with that of flame emission is due to its relative freedom from interferences by inter-element effects and its relative insensitivity to variations in flame temperature. Only for the routine determination of alkali and alkaline earth metals, is flame photometry usually preferred. Over sixty elements can be determined in almost any matrix by atomic absorption. Examples include heavy metals in body fluids, polluted waters, foodstuffs, soft drinks and beer, the analysis of metallurgical and geochemical samples and the determination of many metals in soils, crude oils, petroleum products and plastics. Detection limits generally lie in the range 100-0.1 ppb (Table 8.4) but these can be improved by chemical pre-concentration procedures involving solvent extraction or ion exchange. 

Atomic absorption spectroscopy is highly specific and there are very few cases of interference due to the similar emission lines from different elements. General interference effects, such as anionic and matrix effects, are very similar to those described under flame emission photometry and generally result in reduced absorbance values being recorded. Similarly, the use of high temperature flames may result in reduced absorbance values due to ionization effects. However, ionization of a test element can often be minimized by incorporating an excess of an ionizable metal, e.g. potassium or caesium, in both the standards and samples. This will suppress the ionization of the test element and in effect increase the number of test atoms in the flame. 

One often unsuspected source of error can arise from interference by the substances originating in the sample which are present in addition to the analyte, and which are collectively termed the matrix. The matrix components could enhance, diminish or have no effect on the measured reading, when present within the normal range of concentrations. Atomic absorption spectrophotometry is particularly susceptible to this type of interference, especially with electrothermal atomization. Flame AAS may also be affected by the flame emission or absorption spectrum, even using ac modulated hollow cathode lamp emission and detection (Faithfull, 1971b, 1975). 

It would appear in all cases that measurements should be based on atomic absorption instead of flame emission. Absorption spectra are simpler than emission spectra. In reality, however, the absorption measurements can be complicated by the presence of interferences, chemical interaction, instability of the energy level, and other phenomena that occur at elevated temperatures (Fig. 14.3). 

Analysis by atomic (or optical) emission spectroscopy is based on the study of radiation emitted by atoms in their excited state, ionised by the effect of high temperature. All elements can be measured by this technique, in contrast to conventional flames that only allow the analysis of a limited number of elements. Emission spectra, which are obtained in an electron rich environment, are more complex than in flame emission. Therefore, the optical part of the spectrometer has to be of very high quality to resolve interferences and matrix effects.-... 

The photomultiplier detects both the thermal emission from the determinant and also any other atomic or molecular emission from either concomitant elements present in the sample or from the flame itself. Figure 8, for example, shows a typical section of a flame emission spectrum. While it is possible for some determinations by FES to work at a single fixed wavelength, as in flame AAS, it is advisable, at least initially, to scan the emission spectrum in the vicinity of the wavelength of interest to confirm the absence of spectral interferences. In any event, regular re-zeroing and aspiration of an appropriate standard to check for signal drift is essential. 

Interferences encountered in AAS can be separated into the following categories (A) Spectral. (B) Flame emission. (C) Chemical. (D) Matrix. (E) Non-specific scatter. (F) Ionisation. The majority of difficulties that the analyst can expect to encounter arise from chemical, matrix, light-scattering and ionisation interferences. 

Flame emission techniques generally, require that the monochromator be more strongly resolving than in atomic absorption techniques. In other words the analyst has to use narrower slits in the monochromator. The most effective way to find the best slit to use in a particular instance is to measure the signal-to-noise ratio, that is the percent relative standard deviation for a series of measurements on a suitable standard with each of the slits that are available. The analyst may be surprised to find that in practice the best precision is very often found with extremely narrow spectral bandwidths. This is because unwanted spectral interference is filtered out from the flame. 

Each spectroscopic method has a characteristic application. For example, flame photometry is still applicable to the direct determination of Ca and Sr, and to the determination of Li, Rb, Cs and Ba after preconcentration with ion-exchange resin. Fluorimetry provides better sensitivities for Al, Be, Ga and U, although it suffers from severe interference effects. Emission spectrometry, X-ray fluorescence spectrometry and neutron activation analysis allow multielement analysis of solid samples with pretty good sensitivity and precision, and have commonly been applied to the analysis of marine organisms and sediments. Recently, inductively-coupled plasma (ICP)... 

Before the 1960 s, the analysis of toxic elements in airborne materials employed separations and colorimetric determination for single-element problems, or spectrographic methods for multielement, multisample studies. Variable matrices in most aerosols sampled had prevented sensitive, but interference-prone, flame-emission methods from attaining much usage. The increased concern over the environmental effects of toxic elements in the late 1960 s resulted in a need for greater sensitivity and ease of operation in measurements of these elements. The many laboratories with increased responsibilities found AAS most useful because of its accuracy, sensitivity, and relative lack of matrix effects, plus the low cost of the equipment. 

Where only the determination of alkali metals is desired, a simple instrument can be devised in which selection of a resonance line can be obtained with the help of color filters. However, at present such instruments would not appear to have an appreciable advantage over flame emission methods, considering the sensitivity of the latter and the simplicity of presently available flame photometers. Appreciable advantages, on the other hand, are inherent in absorption over emission methods in the determination of the alkaline earths and magnesium. Since these metals have simple emission spectra, the use of filters, notably interference filters, would be feasible in instruments limited to the determination of these elements. 

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