Atomic absorption spectral analyses

Krishnamurty, K. V. et al., At. Abs. Newslett., 1976, 15, 68-70 When preparing soil and sediment samples for atomic absorption spectral analysis for trace metals, pre-oxidation with nitric acid before addition of hydrogen peroxide eliminates the danger of explosion. 

L vov BV (1966) Atomic absorption spectral analysis. Nauka, Moscow (in Russian)... 

Atomic emission is used for the analysis of the same types of samples that may be analyzed by atomic absorption. The development of a quantitative atomic emission method requires several considerations, including choosing a source for atomization and excitation, selecting a wavelength and slit width, preparing the sample for analysis, minimizing spectral and chemical interferences, and selecting a method of standardization. 

BeryUium aUoys ate usuaUy analyzed by optical emission or atomic absorption spectrophotometry. Low voltage spark emission spectrometry is used for the analysis of most copper-beryUium aUoys. Spectral interferences, other inter-element effects, metaUurgical effects, and sample inhomogeneity can degrade accuracy and precision and must be considered when constmcting a method (17). 

Only arc/spark, plasma emission, plasma mass spectrometry and X-ray emission spectrometry are suitable techniques for qualitative analysis as in each case the relevant spectral ranges can be scanned and studied simply and quickly. Quantitative methods based on the emission of electromagnetic radiation rely on the direct proportionality between emitted intensity and the concentration of the analyte. The exact nature of the relation is complex and varies with the technique it will be discussed more fully in the appropriate sections. Quantitative measurements by atomic absorption spectrometry depend upon a relation which closely resembles the Beer-Lambert law relating to molecular absorption in solution (p. 357 etal.). 

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 presence and concentration of various metallic elements in petroleum coke are major factors in the suitability of the coke for various uses. In the test method (ASTM D5056), a sample of petroleum coke is ashed (thermally decomposed to leave only the ash of the inorganic constituents) at 525°C (977°F). The ash is fused with lithium tetraborate or lithium metaborate. The melt is then dissolved in dilute hydrochloric acid and the resulting solution is analyzed by atomic absorption spectroscopy to determine the metals in the sample. However, spectral interferences may occur when using wavelengths other than those recommended for analysis or when using multielement hollow cathode lamps. 

The basis for the claim of discovery of an element has varied over the centuries. The method of discovery of the chemical elements in the late eightenth and the early nineteenth centuries used the properties of the new sustances, their separability, the colors of their compounds, the shapes of their crystals and their reactivity to determine the existence of new elements. In those early days, atomic weight values were not available, and there was no spectral analysis that would later be supplied by arc, spark, absorption, phosphorescent or x-ray spectra. Also in those days, there were many claims, e.g., the discovery of certain rare earth elements of the lanthanide series, which involved the discovery of a mineral ore, from which an element was later extracted. The honor of discovery has often been accorded not to the person who first isolated the element but to the person who discovered the original mineral itself, even when the ore was impure and that ore actually contained many elements. The reason for this is that in the case of these rare earth elements, the earth now refers to oxides of a metal not to the metal itself This fact was not realized at the time of their discovery, until the English chemist Humphry Davy showed that earths were compounds of oxygen and metals in 1808. 

The atomic absorption characteristics of technetium have been investigated with a technetium hollow-cathode lamp as a spectral line source. The sensitivity for technetium in aqueous solution is 3.0 /ig/ml in a fuel-rich acetylene-air flame for the unresolved 2614.23-2615.87 A doublet under the optimum operating conditions. Only calcium, strontium, and barium cause severe technetium absorption suppression. Cationic interferences are eliminated by adding aluminum to the test solutions. The atomic absorption spectroscopy can be applied to the determination of technetium in uranium and its alloys and also successfully to the analysis of multicomponent samples. 

A convenient method is the spectrometric determination of Li in aqueous solution by atomic absorption spectrometry (AAS), using an acetylene flame—the most common technique for this analyte. The instrument has an emission lamp containing Li, and one of the spectral lines of the emission spectrum is chosen, according to the concentration of the sample, as shown in Table 2. The solution is fed by a nebuhzer into the flame and the absorption caused by the Li atoms in the sample is recorded and converted to a concentration aided by a calibration standard. Possible interference can be expected from alkali metal atoms, for example, airborne trace impurities, that ionize in the flame. These effects are canceled by adding 2000 mg of K per hter of sample matrix. The method covers a wide range of concentrations, from trace analysis at about 20 xg L to brines at about 32 g L as summarized in Table 2. Organic samples have to be mineralized and the inorganic residue dissolved in water. The AAS method for determination of Li in biomedical applications has been reviewed . 

D. The measurement of Li in brine (salt water) is used by geochemists to help determine the origin of this fluid in oil fields. Flame atomic emission and absorption of Li are subject to interference by scattering, ionization, and overlapping spectral emission from other elements. Atomic absorption analysis of replicate samples of a marine sediment gave the results in the table below. 

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. 

Graphite Furnace Atomic Absorption Spectrometry Graphite furnace atomic absorption spectrometry (GFAAS), the most popular form of ET-AAS, is today a common technique widely used in routine laboratories and has become a powerful tool for the analysis of trace and ultratrace elements in clinical and biological samples [61]. The main advantages of this technique are low cost, simplicity, excellent detection power, and the fact that it allows very low sample volumes to be used (5-20 p,L). In this sense, this technique allows LoDs for many elements in the order of 0.01 pgl-1 in solution or 1 pg g-1 in solid samples to be achieved [62]. However, the technique is prone to spectral and matrix interferences. 

The flame is a chemical reaction which takes place in the gas phase. The ideal flame for atomic absorption would generate the correct amount of thermal energy to dissociate the atoms from their chemical bonds. The most commonly used flames are aii -acetylene and nitrous oxide—acetylene. The choice of oxidant depends upon the flame temperature and composition required for the production of free atoms. These temperatures vary the molecular or chemical form of the element. Air and acetylene produce flame temperatures of about 2300°C and permit the analysis by atomic absorption of some thirty or so elements. The nitrous oxide—acetylene flame is some 650°C hotter and extends the atomic absorption technique to around 66 elements. It also permits the successful analysis of most elements by flame atomic emission, in many cases at fractional parts per million levels, providing adequate spectral resolution is available. 

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