Forensic application of laser-induced breakdown spectroscopy for the discrimination of questioned documents

• The analysis of questioned documents using LIBS and LA-ICP-MS are presented.
• LIBS was successful to discriminate papers produced at different time interval.
• Both LIBS and LA-ICP-MS provide excellent discrimination between different printer sources.

Document examination is an important forensic discipline and the legal system regularly needs the knowledge and skills of the scientific expert when questioned documents are involved in criminal or civil matters. Amongst the many aspects of the scientific examination of documents, elemental analysis can provide useful results. In this study, the evaluation of the analytical performance of a commercially available laser-induced breakdown spectroscopy (LIBS) instrument was conducted on office papers, writing inks, inkjet inks and laser printer toners. The paper sample set analysed consisted of 33 Australian paper specimens originating from the same production plant but representing different brands and/or batches. In addition, a total of 131 ink or toner samples were examined that included black and blue ballpoint inks, black inkjet inks, and black laser printer toners originating from several manufacturing sources, models and/or batches. Results from the LIBS method were compared against those obtained using more established elemental profiling method such as laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS). LIBS demonstrated detectable and significant differences between different batches of the same brand as well as between different brands of paper, ink and toner samples. The LIBS method provided comparable discrimination powers for the selected sample sets when compared to those obtained using LA-ICP-MS (discrimination from 99.8 and 100% of the sample pairs, depending on the sample subset under examination). LIBS is a suitable technique for the determination of elemental composition as part of a protocol for the examination of questioned documents.