Atomic spectroscopy, analytical

J. Sneddon, Sample Introduction in Atomic Spectroscopy (Analytical Spectroscopy Library), Elsevier, New York, 1990. 

In atomic spectroscopy, analyte is atomized in a flame, an electrically heated furnace, or a plasma. Flames were used for decades, but they have been replaced by the inductively coupled plasma and the graphite furnace. We begin our discussion with flames because they are still common in teaching labs. 

Bings NH, Bogaerts A, and Broekaert JAC (2002) Atomic spectroscopy. Analytical Chemistry 74 2691-2711. 

Slavin, W. A Gomparison of Atomic Spectroscopic Analytical Techniques, Spectroscopy 1991, 6, 16-21. 

Spectroscopy, aimual reviews of new analytical instmmentation from the Pittsburgh Conference on Analytical Chemistry and AppHed Spectroscopy. Analytical Chemisty, "Fundamental Reviews" (June 1994, June 1996), analytical appHcations of infrared, ultraviolet, atomic absorption, emission, Raman, fluorescence, phosphorescence, chemiluminescence, and x-ray spectroscopy. 

Atomic Spectroscopy and Journal of Analytical Atomic Spectromety, regular and occasional topical bibHographies. 

Analytical Atomic Spectroscopy Surface Analysis," Mnnual Book ofMSTM Standards, part 3.06, American Society for Testing and Matedals, Philadelphia, Pa., 1992. 

Unfortunately, these rather basic errors are distressingly common, yet cause much unnecessary dissatisfaction. No printer is perfect, and relying on catalog data can result in the publication of incorrect data in a paper. This occurred, e.g. in 1994 when data was taken from an out-of-date NIST catalog, rather than the appropriate certificate. Published in the Journal of Analytical Atomic Spectroscopy, the paper by Soares et al. (1994) cited a certified value for Cr in NIST SRM 1548, when consultation of the Certificate would have shown that for several technical reasons the element value reported could not be certified. 

Practically all classical methods of atomic spectroscopy are strongly influenced by interferences and matrix effects. Actually, very few analytical techniques are completely free of interferences. However, with atomic spectroscopy techniques, most of the common interferences have been studied and documented. Interferences are classified conveniently into four categories chemical, physical, background (scattering, absorption) and spectral. There are virtually no spectral interferences in FAAS some form of background correction is required. Matrix effects are more serious. Also GFAAS shows virtually no spectral interferences, but... 

Atomic spectroscopy has been reviewed [92] a recent update is available [93]. An overview of sample introduction in atomic spectrometry is available [94]. Several recent books deal with analytical atomic spectrometry [95-100],... 

Adapted from Moenke-Blankenburg [217]. From L. Moenke-Blanken-burg, in Lasers in Analytical Atomic Spectroscopy (J. Sneddon et al., eds), VCH Publishers, New York, NY (1997), pp. 125-195. Reproduced by permission of Wiley-VCH. 

K. W. Jackson (ed.), Electrothermal Atomization for Analytical Atomic Spectroscopy, John Wiley Sons, Ltd, Chichester (1999). 

G. Schlemmer and B. Radziuk, A Laboratory Guide to Graphite Furnace Analytical Atomic Spectroscopy, Springer-Verlag, Berlin (1998). 

A. Montaser and D.W. Golightly, Inductively Coupled Plasmas in Analytical Atomic Spectroscopy, VCH, New York, NY (1992). 

Young, S. M. M. and M. Pollard (2000), Atomic spectroscopy and spectrometry, in Ciliberto, E. and G. Spoto (eds.), Modern Analytical Methods in Art and Archaeology, Chemical Analysis Series, Vol. 155, Wiley, New York, pp. 21-54. 

A rough gradation of analyte amounts has been done by de Gramont [1922] who investigated 82 elements in minerals, ores and alloys by means of atomic spectroscopy using so-called ctraies ultimes (last lines, ultimate lines, i.e. such lines which disappear at definite concentrations). 

The signal-to-noise ratio has been used in analytical chemistry since the 1960s. At first, atomic spectroscopy prepared the way for application, and some other spectroscopic disciplines and chromatography are important domains of use. 

Katsibiri O., Boon J.J., Investigation of the gilding technique in two post Byzantine wall paintings using micro analytical techniques, Spectrochimica Acta, Part B Atomic Spectroscopy, 2004, 59B, 1593 1599. 

Determination of trace metals in seawater represents one of the most challenging tasks in chemical analysis because the parts per billion (ppb) or sub-ppb levels of analyte are very susceptible to matrix interference from alkali or alkaline-earth metals and their associated counterions. For instance, the alkali metals tend to affect the atomisation and the ionisation equilibrium process in atomic spectroscopy, and the associated counterions such as the chloride ions might be preferentially adsorbed onto the electrode surface to give some undesirable electrochemical side reactions in voltammetric analysis. Thus, most current methods for seawater analysis employ some kind of analyte preconcentration along with matrix rejection techniques. These preconcentration techniques include coprecipitation, solvent extraction, column adsorption, electrodeposition, and Donnan dialysis. 

Slavin, W. (1992). A comparison of atomic spectroscopic analytical techniques. Spectroscopy International 4 22-27. 

Elemental analysis at the trace or ultratrace level can be performed by a number of analytical techniques however, atomic spectroscopy remains... 

All reagents and solvents that are used to prepare the sample for analysis should be ultrapure to prevent contamination of the sample with impurities. Plastic ware should be avoided since these materials may contain ultratrace elements that can be leached into the analyte solutions. Chemically cleaned glassware is recommended for all sample preparation procedures. Liquid samples can be analyzed directly or after dilution when the concentrations are too high. Remember, all analytical errors are multiplied by dilution factors therefore, using atomic spectroscopy to determine high concentrations of elements may be less accurate than classical gravimetric methods. 

The selection of a technique to determine the concentration of a given element is often based on the availability of the instrumentation and the personal preferences of the analytical chemist. As a general rule, AAS is preferred when quantifications of only a few elements are required since it is easy to operate and is relatively inexpensive. A comparison of the detection limits that can be obtained by atomic spectroscopy with various atom reservoirs is contained in Table 8.1. These data show the advantages of individual techniques and also the improvements in detection limits that can be obtained with different atom reservoirs. 

On the basis of the preceding discussion, it should be obvious that ultratrace elemental analysis can be performed without any major problems by atomic spectroscopy. A major disadvantage with elemental analysis is that it does not provide information on element speciation. Speciation has major significance since it can define whether the element can become bioavailable. For example, complexed iron will be metabolized more readily than unbound iron and the measure of total iron in the sample will not discriminate between the available and nonavailable forms. There are many other similar examples and analytical procedures that must be developed which will enable elemental speciation to be performed. Liquid chromatographic procedures (either ion-exchange, ion-pair, liquid-solid, or liquid-liquid chromatography) are the best methods to speciate samples since they can separate solutes on the basis of a number of parameters. Chromatographic separation can be used as part of the sample preparation step and the column effluent can be monitored with atomic spectroscopy. This mode of operation combines the excellent separation characteristics with the element selectivity of atomic spectroscopy. AAS with a flame as the atom reservoir or AES with an inductively coupled plasma have been used successfully to speciate various ultratrace elements. 

R.M. Harrison and S. Raposomanikos, Environmental Analysis using Chromatography Interfaced with Atomic Spectroscopy, Ellis Horwood Series in Analytical Chemistry, Ellis Horwood Ltd., Chichester, 1992. 

Analytical Chemistry. Particularly the biennial reviews of atomic spectroscopy that are published in the even years. 

Evans, R. D. and Outridge, P. M. (1994). Applications of laser ablation inductively coupled plasma mass spectrometry to the determination of environmental contaminants in calcified biological structures. Journal of Analytical Atomic Spectroscopy 9 985-989. 

Raith, A., Hutton, R. C., Abell, I. D., and Crighton, J. (1995). Non-destructive sampling method of metals and alloys for laser ablation-inductively coupled plasma mass spectrometry. Journal of Analytical Atomic Spectroscopy 10 591-594. 

Roberts, N.B, Walsh, H.P.J., Klenerman, L., Kelly, S.A., and Helliwell, T. R. (1996). Determination of elements in human femoral bone using inductively coupled plasma atomic emission spectrometry and inductively coupled plasma mass spectrometry. Journal of Analytical Atomic Spectroscopy 11 133-138. 

Watling, R. J., Lynch, B. F., and Herring, D. (1997). Use of laser ablation inductively coupled plasma mass spectrometry for fingerprinting scene of crime evidence. Journal of Analytical Atomic Spectroscopy 12 195-203. 

Schrenk, W.G. (1975) Modern Analytical Chemistry. Analytical Atomic Spectroscopy. Plenum Press, New York. 

---