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Plasma Diagnostics through Kinetic Modelling: Characterization of Matrix Effects during ICP and Flame Atomic Spectrometry in terms of Collisional Radiative Recombination Activation Energy–A Review

Mark Fungayi Zaranyika and Courtie Mahamadi

Inductively coupled plasma atomic emission spectrometry (ICP-AES) is one of the most widely used and extremely important tools for trace element analysis today. The technique however still suffers from matrix effects, especially those due to easily ionizable elements (EIEs). Current theory of atomic spectrometry assumes Local Thermal Equilibrium (LTE), and EIE interference effects cannot be explained fully as long as all the electrons in the plasma are regarded as equivalent in accordance with the LTE theory. If however it is assumed that electronic collisions with heavy particles can occur before or after thermal equilibration, then electrons can be expected to experience different activation energies depending on whether collisions occurred before or after thermal equilibration. This paper reviews recent work carried out to characterize EIE interference effects during ICP-AES, flame AAS and flame AES in terms of ion-electron collisional radiative recombination activation energy. The work is based on a simplified rate model showing that when analytes are determined by atomic spectrometry in the absence and then in the presence of EIEs as interferents, the change in collisional radiative recombination activation energy, ΔEa, is zero when the system conforms to LTE. Several analyte-interferent systems have been studied, and results obtained so far lead to the conclusion that departure from LTE results from collisions involving electrons in the ambipolar diffusion state. Factors affecting both pre-LTE and LTE collisions, as well as a possible collisional radiative recombination mechanism designed to account for the ΔEa values obtained are discussed.