Forensic classification of black inkjet prints using Fourier transform near-infrared spectroscopy and Linear Discriminant Analysis.

This work presents a study regarding the forensic discrimination of black inkjet-printed documents in question. Nondestructive Fourier transform near-infrared (FT-NIR) spectroscopy in combination with supervised classification method Discriminant Analysis (DA); Linear Discriminant Analysis (LDA) and Quadratic Discriminant Analysis (QDA) were utilized to investigate 22 different prints of the three most sold office printer brands. The spectra were acquired using the FT-NIR spectrometer NIRFlex N-500 (Büchi Labortechnik AG, Flawil, Switzerland) with the Fiber Optic Solids measuring cell in the spectral region of 10,000-4000 cm-1. Each sample was printed on the same type of office paper. The spectra were 45 times acquired on 3 separate printed squares of each sample. It results in 990 acquired spectra for the presented experiment. The FT-NIR spectra of the printed squares were split into calibration and test sets with which the Classification accuracy (CA) value of unknown samples was evaluated. In order to increase the significance, three different compilations of calibration and test sets were realized. The performance of three different Discriminant model methods; LDA (Euclidean and Mahalanobis algorithm) and QDA were compared to each other. Furthermore, the CA of each DA method was examined using 1-5 principal components (PCs) in the construction of the respective DA model. Two groups of models, according to the ink subset (Carbon black and Black colorant), were performed in raw and Standard Normal Variate (SNV) correction spectra alternations. The results showed that the Euclidean method yielded the highest accuracy in predicting independent test samples and thus clearly outperformed the QDA and Mahalanobis algorithm DA method. It was also determined that the ink type Carbon black had higher CA values than the ink type Black colorant. This work demonstrated the special ability of FT-NIR spectroscopy in combination with DA to examine inkjet-printed documents in a fast and non-destructive fashion.

Principal component analysis for the forensic discrimination of black inkjet inks based on the Vis-NIR fibre optics reflection spectra.

Nineteen black inkjet inks of six different brands were examined by fibre optics reflection spectroscopy in Visible and Near Infrared Region (Vis-NIR FORS) directly on paper with a view to achieving good resolution between them. These different inks were tested on nineteen different inkjet printers from three brands. Samples were obtained from prints by reflection probe. Processed reflection spectra in the range 500-1000 nm were used as samples in principal component analysis. Variability between spectra of the same ink obtained from different prints, as well as between spectra of square areas and lines was examined. For both spectra obtained from square areas and lines reference, Principal Component Analysis (PCA) models were created. According to these models, the inkjet inks were divided into clusters. PCA method is able to separate inks containing carbon black as main colorant from the other inks using other colorants. Some spectra were recorded from another piece of printer and used as validation samples. Spectra of validation samples were projected onto reference PCA models. According to position of validation samples in score plots it can be concluded that PCA based on Vis-NIR FORS can reliably differentiate inkjet inks which are included in the reference database. The presented method appears to be a suitable tool for forensic examination of questioned documents containing inkjet inks. Inkjet inks spectra were obtained without extraction or cutting sample with possibility to measure out of the laboratory.

Chemometric tool for identification of iron-gall inks by use of visible-near infrared fibre optic reflection spectroscopy.

A method has been developed for identification of corrosive iron-gall inks in historical drawings and documents. The method is based on target-factor analysis of visible-near infrared fibre optic reflection spectra (VIS-NIR FORS). A set of reference spectra was obtained from model samples of laboratory-prepared inks covering a wide range of mixing ratios of basic ink components deposited on substrates and artificially aged. As criteria for correspondence of a studied spectrum with a reference spectrum, the apparent error in target (AET) and the empirical function SPOIL according to Malinowski were used. The capability of the proposed tool to distinguish corrosive iron-gall inks from bistre and sepia inks was evaluated by use of a set of control samples of bistre, sepia, and iron-gall inks. Examples are presented of analysis of historical drawings from the 15th and 16th centuries and written documents from the 19th century. The results of analysis based on the tool were confirmed by XRF analysis and colorimetric spot analysis.