Evaluating the potential of near infrared hyperspectral imaging associated with multivariate data analysis for examining crossing ink lines.

The determination of the chronological sequence of crossing ink lines is a recurrent issue in the forensic examination of questioned documents. This manuscript intends to evaluate the potential of hyperspectral imaging in the near infrared range (HSI-NIR) combined with multivariate data analysis for rapid, objective and nondestructive analysis of crossing ink lines made with black pens. Twenty-one black gel and ballpoint pens from different brands and models were employed to prepare crossing combinations in both orders in white office paper. An initial pre-selection and extraction step using the Principal Components Analysis (PCA) scores plot arranged as histograms was necessary for extracting the inks spectra. Then, Partial Least Squares-Discriminant Analysis (PLS-DA) was applied for selection of the most important variables. Multivariate Curve Resolution-Alternating Least Squares (MCR-ALS) in the augmented form was performed using both the raw and the pre-processed spectra. However, the pre-processing of spectra resulted in incorrect identification of pixels in the inks distribution maps. The MCR-ALS results obtained using the raw spectra allowed the correct determination of the order of crossings in only one pair of gel-gel pen crossings. The remainder were either impossible to discriminate ink from paper or the skipping of one pen ink line led to incorrect determinations in one of the orders. In spite of the practical advantages of the HSI-NIR for document examination and the different chemometric approaches considered for surpassing some of the spectral limitations, the results obtained demonstrate the difficulties of using this technology for application in real forensic cases.