Modeling and separation-detection methods to evaluate the speciation of metals for toxicity assessment.

There is an increasing appreciation for the importance of speciation in the assessment of metal toxicity. In this review, two approaches to speciation are discussed, with an emphasis on their application to biological samples. One approach is the direct separation and detection of metal species of toxicological interest. Various "hyphenated" techniques, consisting of a chromatographic system coupled to inductively coupled plasma-mass spectrometry (ICP-MS), are discussed. The chromatographic strategies employed for separation emphasize liquid chromatography (LC), but the increasing use of gas chromatography (GC) and capillary electrophoresis (CE) in speciation analysis is discussed. The second approach to speciation is the use of computer models to calculate the speciation of a metal ion within a complex mixture of ligands. This approach is applicable to systems in which the metal cation exchanges ligands rapidly, so that the sample represents an equilibrium mixture of metal complexes. These computational models are based on the equilibrium constants for the metal complexes and a series of mass balance equations and give the distribution of metal complexes in the original sample. This approach is illustrated using the speciation of Al(III) in serum as an example.