Detection of organic and inorganic gunshot residues from hands using complexing agents and LC-MS/MS

Abstract

Gunshot residue (GSR) refers to a conglomerate consisting of both organic molecules (OGSR) and inorganic species (IGSR). Historically, forensic examiners have focused only on identifying the IGSR particles by their morphology and elemental composition. Nonetheless, modern ammunition formulations and challenges with the GSR transference (such as secondary and tertiary transfer) have driven research efforts for more comprehensive examinations, requiring alternative analytical techniques. This study proposes the use of LC-MS/MS for chromatographic separation and dual detection of inorganic and organic residues. The detection of both target species in the same sample increases the confidence that chemical profiles came from a gun's discharge instead of non-firearm-related sources. This strategy implements supramolecular molecules that complex with the IGSR species, allowing them to elute from the column towards the mass spectrometer while retaining isotopic ratios for quick and unambiguous identification. The macrocycle (18-crown-6-ether) complexes with lead and barium, while antimony complexes with a chelating agent (tartaric acid). The total analysis time for OGSR and IGSR in one sample is under 20 minutes. This manuscript expands from a previous proof-of-concept publication by improving figures of merit, increasing the target analytes, testing the method's feasibility through a more extensive set of authentic specimens collected from the hands of both shooters and non-shooters, and comparing performance with other analytical techniques such as ICP-MS, electrochemical methods and LIBS. The linear dynamic ranges (LDR) spread across the low ppb range for OGSR (0.3–200 ppb) and low ppm range (0.1–6.0 ppm) for IGSR. The method's accuracy increased overall when both organic and inorganic profiles were combined.