Forensic differentiation of blue pen inks using time-of-flight secondary ion mass spectrometry and multivariate statistical methods

• First use of ToF-SIMS with PCA and MCR for forensic ink analysis. • Clear differentiation of six blue pen inks via advanced statistical methods. • Non-destructive identification of pen strokes in forgery cases. • MCR provides exact pen stroke ID based on unique spectral signals. • Detailed spatial analysis of pen strokes using large-area ToF-SIMS imaging. This study investigates the use of time-of-flight secondary ion mass spectrometry (ToF-SIMS) combined with multivariate statistical analysis for the identification of blue pen strokes in document forgery cases. Strokes of six commercially available blue pens were analysed using ToF-SIMS, and the data were interpreted using principal component analysis (PCA) and multivariate curve resolution (MCR). PCA effectively reduced the dimensionality of the complex ToF-SIMS data, enabling clear differentiation of the blue pen inks based on the obtained PCA scores. The first three principal components accounted for most of the variance, with PCA score plots showing distinct clusters of samples corresponding to the spectra of each pen. PCA analysis of the large-area ToF-SIMS images further revealed some characteristic spatial patterns and variations across the pen strokes; however, this analysis was less useful for the identification process. On the other hand, MCR provided a more chemically intuitive analysis by extracting pure component spectra from the complex mixtures. Each MCR factor was individually associated with a specific pen, allowing for exact identification of the pen stroke made. MCR score images displayed clear correlations with individual pen strokes, and the associated loadings identified signals at particular m / z values that were characteristic of each pen. This study shows that an efficient method for non-destructive forensic analysis of blue pen strokes can be achieved by combining ToF-SIMS with PCA and MCR. This analytical method provides reliable identification, which is crucial for forgery detection without requiring any sample pretreatment, i.e. the samples (pen strokes) were used just as they were made on paper.