From Calibration-Free to Fundamental Parameters Analysis: A comparison of three recently proposed approaches

In this paper, we present a discussion on three different methods recently proposed for the analysis of Laser-Induced Breakdown Spectroscopy (LIBS) spectra, namely the One-Point-Calibration, the Calibration-Free Inverse method, and the Csigma graphs approach. The common characteristics of these methods is the fact of being based on the main equations governing the emission of near-LTE plasmas, i.e. the same theoretical framework that is at the basis of the Calibration-Free LIBS analysis. However, with the purpose to guarantee a higher trueness in the analysis, these methods rely on the information obtained by the analysis of a single reference material, of known composition, for calculating the values of some experimental parameters that would be otherwise difficult to determine. In analogy with a similar approach used in the analysis of X-ray Fluorescence spectra, we place these techniques in the general framework of the so-called Fundamental Parameters Analysis. The three methods were tested and compared on LIBS spectra acquired on modern bronze samples. The advantages and drawbacks of the different approaches are discussed in detail. - Highlights: • Three analytical methods, based on the equations of LTE plasmas, are compared and discussed. • All these methods rely on the use of a single standard of known composition. • The methods were tested on LIBS spectra acquired on modern bronze samples. • The advantages and drawbacks of the different approaches are discussed in detail.