Discrimination of paper and print types based on their laser induced breakdown spectra

•The potential of LIBS for the discrimination of paper and print types was assessed.•Six paper types and eight printers (a total of 54 samples) were included in the study.•Data evaluation was done using 3 comparative and 2 multivariate statistical methods.•The MCR-ALS/DA approach, when applied to UV LIBS data, gave best results.•Only one or two LIBS shots are needed for sample discrimination/identification.

In the present work, the analytical potential of laser induced breakdown spectroscopy (LIBS) for the discrimination of paper types and prints made by digital printers on these papers was assessed. Six different paper types (including standard office papers, color paper and non-bleached paper), and eight printers (including laser and inkjet, as well as color and black printers) were included in the study. Only one or two laser shots were delivered to each sample in order to cause minimal sample destruction and provide maximum spatial resolution. The statistical evaluation of LIBS spectra was performed by multiple methods including three comparative functions (linear correlation, sum of squared deviations and overlapping integral) as well as two advanced statistical methods (multivariate curve resolution alternating least squares (MCR-ALS) combined with classification tree and discriminant analysis (DA)). The best classification results were obtained with the newly introduced MCR-ALS/DA approach, which proved to be 96.3% accurate in the identification of the paper type and 83.3% accurate in the identification of the printer type, based on the LIBS spectrum collected from just a single laser shot to the sample. It was found that the UV part of the LIBS spectrum can be used most efficiently for the discrimination.