Targeted and non-targeted forensic profiling of black powder substitutes and gunshot residue using gradient ion chromatography - high resolution mass spectrometry (IC-HRMS).

A novel and simplified gradient IC-HRMS approach is presented in this work for forensic profiling of ionic energetic material residues, including low-order explosives and gunshot residue (GSR). This new method incorporated ethanolic eluents to facilitate direct coupling of IC and HRMS without auxiliary post-column infusion pumps that are traditionally used to assist with gas phase transfer. Ethanolic eluents also enabled better integration with an in-service protocol for direct analysis of high-order organic explosives by IC-HRMS, without requiring solvent exchange before injection. Excellent method performance was achieved, enabling both full scan qualitative and quantitative analysis, as required. In particular, linearity for 19 targeted compounds yielded R > 0.99 across several orders of magnitude, with trace analysis possible at the low-mid pg level. Reproducibility and mass accuracies were also excellent, with peak area %RSDs <10%, t %RSDs <0.4% and δ < 3 ppm. The method was applied to targeted analysis of latent fingermarks and swabbed hand sweat samples to determine contact with a black-powder substitute containing nitrate, benzoate and perchlorate. When combined with principal component analysis (PCA), the effect of time since handling on recorded signals could be interpreted further in order to support forensic investigations. In a second, non-targeted application, PCA using full scan IC-HRMS data enabled classification of GSR from three different types of ammunition. An additional 20 markers of GSR were tentatively identified in silico, in addition to the 15 anions detected during targeted analysis. This new approach therefore streamlines and adds consistency and flexibility to forensic analysis of ionic energetic material. Furthermore, it also has implications for targeted, non-targeted and suspect screening applications in other fields by expanding the separation space to low molecular weight inorganic and organic anions.