Chemometrics-Assisted Calibration of a Handheld LIBS Device for the Quantitative Determination of Major and Minor Elements in Artifacts from the Archaeological Park of Tindari (Italy)

In this study, a chemometrics-assisted calibration method was developed for the Z-903 SciAps handheld Laser-Induced Breakdown Spectroscopy (h-LIBS) device. For this purpose, seventeen silica-based standard samples with known chemical composition were collected, pelleted, and analyzed using h-LIBS. Spectral data were pre-processed using a Whittaker filter and normalized via Standard Normal Variate (SNV). The dataset was divided into calibration and validation sets using the Kennard–Stone algorithm. Partial Least Square (PLS) regression was employed for multivariate regression analysis, and a variable selection method (i.e., Variable Importance in Projection, VIP) was applied to reduce the number of predictors. Results from the PLS-VIP approach demonstrated that this device is suitable for the quantitative measurement of nineteen chemical elements, including major and minor elements, achieving significant R2 values for major elements including Na (R2 = 0.91), Mg (R2 = 0.95), and Si (R2 = 0.89). The limits of detection reached are satisfying, being, for example, 0.24%, 0.41%, 0.43%, 1.5%, and 1.7% for Na, Al, Ca, Si, and Fe, respectively, among major elements, and 189 ppm, 165 ppm, 203 ppm, and 1 ppm for Ba, Cu, Mn, and Rb, respectively, among minor elements. Uncertainties in prediction of the element concentrations were compared with data from the literature, and the effect of another baseline pretreatment algorithm, airPLS (adaptive iteratively reweighted PLS), was also tested. The method was then applied to nine silica-based artifacts of different typologies sampled from the Archaeological Park of Tindari (Italy), including bricks from the theatre, archaeological glasses, and volcanic rocks.