Solid-state speciation analysis

Principles and Characteristics The fastest growing area in elemental analysis is in the use of hyphenated techniques for speciation measurement. Elemental spe-ciation analysis, defined as the qualitative identification and quantitative determination of the individual chemical forms that comprise the total concentration of an element in a sample, has become an important field of research in analytical chemistry. Speciation or the process yielding evidence of the molecular form of an analyte, has relevance in the fields of food, the environment, and occupational health analysis, and involves analytical chemists as well as legislators. The environmental and toxicological effects of a metal often depend on its forms. The determination of the total metal content 

Speciation involves a number of discrete analytical steps comprising the extraction (isolation) of the analytes from a solid sample, preconcentration (to gain sensitivity), and eventually derivatisation (e.g. for ionic compounds), separation and detection. Various problems can occur in any of these steps. The entire analytical procedure should be carefully controlled in such a way that decay of unstable species does not occur. For speciation analysis, there is the risk that the chemical species can convert so that a false distribution is determined. In general, the accuracy of the determinations and the trace-ability of the overall analytical process are insufficiently ensured [539]. 

Since the concentrations of the various compounds or oxidation states in which trace elements can occur are always lower than the total content of the analyte, speciation analysis is normally an ultratrace determination in the ng L-1 range for solutions and the ng g 1 range for 

Separation technique Element-selective detection techniques 

Element-specific detection Molecular-specific detection 

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Sodium-silicate glass, 151 Sol-gel films, 120, 173 Solid electrodes, 110 Solid state devices, 160 Solvents, 102 Speciation, 84 Spectroelectrochenristry, 40 Spherical electrode, 6, 8, 9, 61 Square-wave voltammetry, 72, 92 Staircase voltammetry, 74 Standard potential, 3 Standard rate constant, 12, 18 Stripping analysis, 75, 79, 110 Supporting electrolyte, 102 Surface-active agents, 79... 

Applications Table 8.58 shows the main fields of application of inorganic mass spectrometry. Mass-spectrometric techniques find wide application in inorganic analysis, and are being used for the determination of elemental concentrations and of isotopic abundances for speciation and surface characterisation for imaging and depth profiling. Solid-state mass spectrometry is usable as a quantitative method only after calibration by standard samples. 

Spectrophotometric methods applicable to speciation analysis for V in different oxidation states have been reviewed [12]. Attempts to speciation of V(IV) and V(V) with Eriochrome Cyanine R in natural waters by solid-phase spectrophotometry has been described... 

Advantages brought about by the direct analysis of solid samples as compared with the analysis of dissolved samples include a shorter total analysis time (prior dissolution steps are not required), low cost (chemical reagents are not used), less risk of contamination and less destruction of the sample. In addition, some techniques can extract information about chemical speciation e.g. XPS provides information about oxidation states and chemical bonds) and spatial composition, i.e. information with lateral resolution allowing mapping of the surface and analysis with depth resolution, of particular interest for thin-film analysis. 

A variety of methods have been used to characterize the solubility-limiting radionuclide solids and the nature of sorbed species at the solid/water interface in experimental studies. Electron microscopy and standard X-ray diffraction techniques can be used to identify some of the solids from precipitation experiments. X-ray absorption spectroscopy (XAS) can be used to obtain structural information on solids and is particularly useful for investigating noncrystalline and polymeric actinide compounds that cannot be characterized by X-ray diffraction analysis (Silva and Nitsche, 1995). X-ray absorption near edge spectroscopy (XANES) can provide information about the oxidation state and local structure of actinides in solution, solids, or at the solution/ solid interface. For example, Bertsch et al. (1994) used this technique to investigate uranium speciation in soils and sediments at uranium processing facilities. Many of the surface spectroscopic techniques have been reviewed recently by Bertsch and Hunter (2001) and Brown et al. (1999). Specihc recent applications of the spectroscopic techniques to radionuclides are described by Runde et al. (2002b). Rai and co-workers have carried out a number of experimental studies of the solubility and speciation of plutonium, neptunium, americium, and uranium that illustrate combinations of various solution and spectroscopic techniques (Rai et al, 1980, 1997, 1998 Felmy et al, 1989, 1990 Xia et al., 2001). 

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