Metals flame atomic emission spectroscopy

Flame atomic emission spectroscopy, also called flame photometry, is based on the measurement of the emission spectrum produced when a solution containing metals or some nonmetals such as halides, sulfur, or phosphorus is introduced into a flame. In early experiments, the detector used was the analyst s eye. Those elements that emitted visible light could be identified qualitatively, and these flame tests were used to confirm the presence of certain elements in the sample, particularly alkali metals and alkaline-earth metals. A list of visible colors emitted by elements in a flame is given in Table 7.1. 

Most alkali and alkaline-earth metal ions that are found dissolved in water are readily quantitated by flame atomic emission spectroscopy (FUAES). This determinative technique has been, in the past, termed flame photometry. A simple photometer uses cutoff filters to isolate the wavelength,... 

Iron metal can be analyzed by x-ray spectroscopy, flame- and furnace atomic absorption, and ICP atomic emission spectroscopy at trace concentration levels. Other instrumental techniques include ICP-mass spectrometry for extreme low detection level and neutron activation analysis. 

Many metal analyses are carried out using atomic spectroscopic methods such as flame or graphite furnace atomic absorption or inductively coupled plasma atomic emission spectroscopy (ICP-AES). These methods commonly require the sample to be presented as a dilute aqueous solution, usually in acid. ICP-mass spectrometry requires similar preparation. Other samples may be analyzed in solid form. For x-ray fluorescence, the solid sample may require dilution with a solid buffer material to produce less variation between samples and standards, reducing matrix effects. A solid sample is also preferred for neutron activation analyses and may be obtained from dilute aqueous samples by precipitation methods. 

Maintaining the quality of food is a far more complex problem than the quality assurance of non-food products. Analytical methods are an indispensable monitoring tool for controlling levels of substances essential for health and also of toxic substances, including heavy metals. The usual techniques for detecting elements in food are flame atomic absorption spectroscopy (FAAS), graphite furnace atomic absorption spectrometry (GF AAS), hydride generation atomic absorption spectrometry (HG AAS), cold vapour atomic absorption spectrometry (CV AAS), inductively coupled plasma atomic emission spectrometry (ICP AES), inductively coupled plasma mass spectrometry (ICP MS) and neutron activation analysis (NAA). 

Atomic spectroscopy is a quantitative technique used for the determination of metals in samples. Atomic spectroscopy is characterized by two main techniques atomic absorption spectroscopy and atomic emission spectroscopy. Atomic absorption spectroscopy (AAS) is normally carried out with a flame (FAAS), although other devices can be used. Atomic emission spectroscopy (AES) is typified by the use of a flame photometer (p. 168) or an inductively coupled plasma. The flame photometer is normally used for elements in groups I and II of the Periodic Table only, i.e. alkali and alkali earth metals. 

Most other metals present in pharmaceuticals are present in sufficient concentrations that high sensitivity is not imperative and they may therefore be determined by flame atomic absorption spectroscopy. These products are extremely variable in composition but nonetheless yield easily to this type of analysis, which is generally unaffected by compounding agents such as binders or expanders. Thus, the elements Na, K, Mg, Ca, Mn, Fe, Co, Cu, Zn, and Mo are among those determinable by flame (51-53) and, recently, furnace (54) atomic absorption in multivitamin-mineral tablets. Chemical interactions between some metals dictate the use of an internal standard when several elements are present simultaneously. It should be noted here that a spark emission or ICP spectrometer equipped with an appropriate polychromator would have the advantage of simultaneous and therefore more rapid analysis in these multielemental products. These techniques have probably not been fully utilized in this regard. 

The determination of trace metal impurities in pharmaceuticals requires a more sensitive methodology. Flame atomic absorption and emission spectroscopy have been the major tools used for this purpose. Metal contaminants such as Pb, Sb, Bi, Ag, Ba, Ni, and Sr have been identified and quantitated by these methods (59,66-68). Specific analysis is necessary for the detection of the presence of palladium in semisynthetic penicillins, where it is used as a catalyst (57), and for silicon in streptomycin (69). Furnace atomic absorption may find a significant role in the determination of known impurities, due to higher sensitivity (Table 2). Atomic absorption is used to detect quantities of known toxic substances in the blood, such as lead (70-72). If the exact impurities are not known, qualitative as well as quantitative analysis is required, and a general multielemental method such as ICP spectrometry with a rapid-scanning monochromator may be utilized. Inductively coupled plasma atomic emission spectroscopy may also be used in the analysis of biological fluids in order to detect contamination by environmental metals such as mercury (73), and to test serum and tissues for the presence of aluminum, lead, cadmium, nickel, and other trace metals (74-77). 

The hottest flames generally used in atomic absorption and emission spectroscopy rarely reach temperatures of 4000 K. It is apparent from the data in Table 10.1 that even at the highest temperature, the excited-state population is very small in comparison to the ground-state population. This is true even for the relatively easily excited alkali metals, which are readily determined by atomic emission spectroscopy. Elements such as zinc show poor sensitivity by atomic emission because an extremely small number of the atoms is thermally excited. 

Several spectroscopic methods have been used to monitor the levels of heavy metals in man, fossil fuels and environment. They include flame atomic absorption spectrometry (AAS), atomic emission spectroscopy (AES), graphite furnace atomic absorption sp>ectrometry (GFAAS), inductively coupled plasma-atomic emission sp>ectroscopy (ICP/AES), inductively coupled plasma mass spectrometry (ICP/MS), x-ray fluorescence sp>ectroscopy (XRFS), isotope dilution mass spectrometry (IDMS), electrothermal atomic absorption spectrometry (ETAAS) e.t.c. Also other spectroscopic methods have been used for analysis of the quality composition of the alternative fuels such as biodiesel. These include Nuclear magnetic resonance spectroscopy (NMR), Near infrared spectroscopy (NIR), inductively coupled plasma optical emission spectrometry (ICP-OES) e.t.c. 

In addition to these induced effects, even undisturbed excited states will not live forever. The general deactivation is a radiationless process. Relatively few molecules exhibit spontaneous emission, called luminescence in the visible, or emission. This deactivation process of the excited state is a statistical effect and does not directly correlate with an act of excitation. Except induced absorption, plasma coupling, hot flames, or sparks can yield a relatively high population in the excited state which will depopulate by emission. This emission is used in analytics, especially in atomic emission spectroscopy. Since atoms in the gases are not influenced by the surrounding and their energies are not smeared by vibrational interactions, they will exhibit sharp characteristic lines for different metals. The advantages are discussed in more detail in Chap. 6 of this book. 

Analytical methods of atomic spectroscopy have been used in forestry and wood product research since their earliest development. Nowadays, almost all of the spectroscopic techniques available are employed in the analysis of metals and trace elements in diverse samples of industrial and environmental origin. The techniques that find most regular application include flame atomic absorption spectroscopy (F-AAS), graphite furnace atomic absorption spectroscopy (GF-AAS), inductively coupled plasma atomic emission spectroscopy (ICP-AES) and, occasionally, also direct current plasma atomic emission spectroscopy (DCP-AES). In many applications F-AAS is a sufficiently sensitive and precise technique however, in the analysis of some environmental samples for trace elements (forest soils, plant material and water) where concentrations may be very low (of the order of 100 ng mL" ) the greater sensitivity of GF-AAS and ICP/DCP-AES is required. In considering the applications of atomic spectroscopy to forestry and... 

All the alkali metals have characteristic flame colorations due to the ready excitation of the outermost electron, and this is the basis of their analytical determination by flame photometry or atomic absorption spectroscopy. The colours and principal emission (or absorption) wavelengths, X, are given below but it should be noted that these lines do not all refer to the same transition for example, the Na D-line doublet at 589.0, 589.6 nm arises from the 3s — 3p transition in Na atoms formed by reduction of Na+ in the flame, whereas the red line for lithium is associated with the short-lived species LiOH. 

Essentially the same spectrometer as is used in atomic absorption spectroscopy can also be used to record atomic emission data, simply by omitting the hollow cathode lamp as the source of the radiation. The excited atoms in the flame will then radiate, rather than absorb, and the intensity of the emission is measured via the monochromator and the photomultiplier detector. At the temperature achieved in the flame, however, very few of the atoms are in the excited state ( 10% for Cs, 0.1% for Ca), so the sample atoms are not normally sufficiently excited to give adequate emission intensity, except for the alkali metals (which are often equally well determined by emission as by absorption). Nevertheless, it can be useful in cases where elements are required for which no lamp is available, although some elements exhibit virtually no emission characteristics at these temperatures. 

Metallic salts (or metallic compounds) after dissolution in appropriate solvents when introduced into a flame (for instance acetylene burning in oxygen at 3200°C), turns into its vapours that essentially contain mostly the atoms of the metal. Quite a few such gaseous metal atoms are usually raised to a particular high energy level that enables them to allow the emission of radiation characteristics features of the metal for example-the characteristic flame colourations of metals frequently encountered in simple organic compounds such as Na-yellow, Ca-brick-red Ba-apple-green. This forms the fundamental basis of initially called Flame Photometry, but more recently known as Flame Emission Spectroscopy (FES). 

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. 

Atomic absorption and flame emission spectroscopy, also called flame photometry, are two methods of quantitative analysis that can be used to measure approximately 70 elements (metals and non-metals). Many models of these instruments allow measurements to be conducted by these two techniques, which rely on different principles. Their applications are numerous, as concentrations in the mg/l (ppm) region or lower can be accessed. 

Investigation of atomic spectra yields atomic energy levels. An important chemical application of atomic spectroscopy is in elemental analysis. Atomic absorption spectroscopy and emission spectroscopy are used for rapid, accurate quantitative analysis of most metals and some nonmetals, and have replaced the older, wet methods of analysis in many applications. One compares the intensity of a spectral line of the element being analyzed with a standard line of known intensity. In atomic absorption spectroscopy, a flame is used to vaporize the sample in emission spectroscopy, one passes a powerful electric discharge through the sample or uses a flame to produce the spectrum. Atomic spectroscopy is used clinically in the determination of Ca, Mg, K, Na, and Pb in blood samples. For details, see Robinson. 

In 1952, Walsh in Australia realized the inherent advantages of atomic absorption spectroscopy over methods based on flame emission for quantitative analysis, and he has given a personal account of the development of the technique.197 Walsh s death in 1998 resulted in a memorial issue of the journal Spectrochimica Acta (B). As well as a brief biography of Walsh and a list of his publications, this contained 22 papers on all aspects of the history of atomic absorption spectroscopy. Together they constitute a valuable record of the birth of this important technique, the difficulties of bringing satisfactory instruments to market, and the history of the application of the method to quantify metals in a wide variety of materials and environments.198... 

When new analytical tools become available, more often than not considerations of responsibility to the patient, practicality, and economy will keep the clinical chemist from accepting such newly developed techniques without careful deliberation. It appears that presently atomic abso tion spectroscopy is slowly finding entrance into medical research and service laboratories, and there is reason to expect that this technique will find wider use and greater application than emission flame spectroscopy. Virtually all metals, with very few exceptions, can be determined by atomic absorption spectroscopy. It is anticipated that this technique not only will replace currently used analytical methods for metals, but will also make feasible the routine determination of elements now impractical by conventional means. Furthermore, the operational stability of available instruments and the simplicity of actual performance of measiurements make this technique well suited for automation, by addition of an automatic sample feed and automatic recording. 

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