Building and analyzing models from data by stirred tank experiments for investigation of matrix effects caused by inorganic matrices and selection of internal standards in Inductively Coupled Plasma-Atomic Emission Spectroscopy

Interfering effects caused by inorganic matrices (inorganic acids as well as easily ionized elements) in inductively coupled plasma-atomic emission spectroscopy have been modeled by regression analysis of experimental data obtained using the "stirred tank method". The main components of the experimental setup were a magnetically-stirred container and two peristaltic pumps. In this way the matrix composition was gradually and automatically varied, while the analyte concentration remained unchanged throughout the experiment. An inductively coupled plasma spectrometer with multichannel detection based on coupled charge device was used to simultaneously measure the emission signal at several wavelengths when the matrix concentration was modified. Up to 50 different concentrations were evaluated in a period of time of 10 min. Both single interfering species (nitric, hydrochloric and sulphuric acids, sodium and calcium) and different mixtures (aqua regia, sulfonitric mixture, sodium-calcium mixture and sodium-nitric acid mixture) were investigated. The dependence of the emission signal on acid concentration was well-fitted by logarithmic models. Conversely, for the easily ionized elements, 3-order polynomial models were more suitable to describe the trends. Then, the coefficients of these models were used as "signatures" of the matrix-related signal variations and analyzed by principal component analysis. Similarities and differences among the emission lines were highlighted and discussed, providing a new insight into the interference phenomena, mainly with regards to the combined effect of concomitants. The combination of the huge amount of data obtained by the stirred tank method in a short period of time and the speed of analysis of principal component analysis provided a judicious means for the selection of the optimal internal standard in inductively coupled plasma-atomic emission spectroscopy. (C) 2008 Elsevier B.V. All rights reserved.