Improving Quantitative Analysis of Lithium in Brines Using Laser-Induced Breakdown Spectroscopy with τ–Algorithm (τLIBS)

In this work, a quantitative analysis of Li in natural brines was carried out by laser-induced breakdown spectroscopy (LIBS) assisted by the τ–algorithm for detailed analysis of the experimental line shapes (τLIBS). Brine samples were collected from different salars located in the Puna plateau (Northwest Argentina) and analyzed by LIBS in the form of solid pressed pellets. The emission intensities of Li I, Hα, and Mg I–II lines were measured and spatially integrated along the line of sight with temporal resolution by using a high-spectral-resolution spectrometer equipped with an intensified charge-coupled device (iCCD) detector. The plasma was characterized through the determination of the electron density and the temperature. The τ–algorithm calculated the optical thicknesses of the Li I lines to generate synthetic intensity profiles that were subsequently fitted to the experimental spectra. By applying the developed τLIBS approach, valuable spectroscopic insight was recovered about the physical processes occurring in the plasma, such as self-absorption. The analytical process involved an univariate external calibration process using the resonant Li I line at 6707.7 Å measured from a series of Li standard samples. Self-absorption effects were evaluated and subsequently compensated. The final LIBS results, with an enhanced accuracy of 15%, were validated by crosschecking them against those obtained with the standard AAS method.