On the Possibility of Universal Chemometric Calibration in X-ray Fluorescence Spectrometry: Case Study with Ore and Steel Samples

Abstract

The accuracy of X-ray fluorescence spectrometry in quantitative element analysis depends on the particular sample composition (so-called matrix effects). Counteracting these effects requires a large number of calibration samples similar in composition to those under analysis. Application of the model constructed for a particular type of samples is not possible for the analysis of samples having a different matrix composition. A possible solution for this problem can be found in the construction of universal calibration models. We propose the development of these universal models using chemometric tools: influence coefficients—partial least squares regression (IC-PLS) and nonlinear kernel regularized least squares regression. We hypothesize that the application of these methods for constructing calibration models would allow embracing the samples of different types in the framework of a single model. We explored this approach for the case of two substantially different types of samples: ores and steels. The performance of these methods was compared with the fundamental parameters (FP) method, which takes into account matrix effects using theoretical equations and allows handling samples of different elemental composition. IC-PLS significantly outperforms traditional FP in terms of accuracy for predicting the content of Al (root mean squared error of prediction 0.96% vs. 3.87%) and Ti (0.05% vs. 0.09%) and yields comparable results for Si and Mn quantification in ores and steels.