Elemental Characterization of Leaded and Lead-Free Inorganic Primer Gunshot Residue Standards Using Single Particle Inductively Coupled Plasma Time-of-Flight Mass Spectrometry.

This study describes the use of single particle inductively coupled plasma time-of-flight mass spectrometry (spICP-TOFMS) for the detection and classification of inorganic gunshot residue (IGSR) particles. To establish reliable multi-element criteria to classify IGSR particles, leaded and lead-free IGSR reference materials were analyzed, and the elemental compositions of the individual particles were quantified. The results suggest that expanded element compositions may be used to classify IGSR particles via spICP-TOFMS compared to those used in conventional IGSR analysis using scanning electron microscopy energy dispersive X-ray spectroscopy (SEM-EDS). For spICP-TOFMS analysis of leaded IGSR particles, classification may be based on the presence of lead (Pb), antimony (Sb), and barium (Ba) just as in SEM-EDS; however, additional particle types, such as lead-copper (Pb-Cu) particles, contribute significantly (∼30%) to the leaded IGSR particle population. In lead-free IGSR particles, the dominate multi-metal particle composition found is titanium-zinc (Ti-Zn) with a conserved Zn:Ti ratio of 1.4:1, but other elements, such as copper (Cu), are also characteristic. In mixtures of the two IGSR reference materials, we were able to classify over 80% of the multi-metal particles detected with no false-positive particle-type assignments. With spICP-TOFMS, particles smaller than those typically measured by SEM-EDS are detected, with estimated median diameters for leaded and lead-free IGSR of 180 and 320 nm, respectively. Through measuring these smaller particles, up to ∼two times more particles per mL are recorded by spICP-TOFMS compared to that found by SEM-EDS. Overall, high-sensitivity and high-throughput analysis using spICP-TOFMS enables quantitative, rapid multi-elemental characterization, and classification of individual IGSR particles.

Analysis of primer gunshot residue particles by laser induced breakdown spectroscopy and laser ablation inductively coupled plasma mass spectrometry.

This study reports novel approaches for the detection of gunshot residues (GSR) from the hands of individuals using Laser-Induced Breakdown Spectroscopy (LIBS) and Laser Ablation Inductively Coupled Plasma Mass Spectrometry (LA-ICP-MS). The methods' performance was evaluated using 159 GSR standard and authentic samples. Forty specimens generated from characterized microparticles were used as matrix-matched primer gunshot residue (pGSR) standards to examine the elemental profiles of leaded and lead-free residues, compared to SEM-EDS and solution-ICP-MS. Also, 119 authentic skin samples were analyzed to estimate error rates. Shooter samples were correctly classified into three categories based on their elemental composition (leaded, lead-free, or mixed pGSR). A total of 60 non-shooter samples were used to establish background thresholds and estimate specificity (93.4% for LA-ICP-MS and 100% for LIBS). All the authentic leaded items resulted in the detection of particle(s) with composition characteristic of pGSR (Pb-Ba-Sb), as observed by simultaneous elemental identification of target analytes at the exact ablation times and locations. When considering the pre-characterized elemental composition of these primers as the "ground truth", LA-ICP-MS resulted in 91.8% sensitivity (true positive rate), while LIBS resulted in 89.2% sensitivity. Particles containing Ba, Bi, Bi-Cu-K, and Cu-Ti-Zn were found in the lead-free residues. Identification of lead-free GSR proved more challenging as some of these elements are common in the environment, resulting in 85.2% sensitivity for LA-ICP-MS and 44.4% for LIBS. Overall accuracies of 94.9% and 88.2% were obtained for the LA-ICP-MS and LIBS sets, respectively. LA-ICP-MS provided an additional level of confidence in the results by its superior analytical capabilities, complementing the LIBS chemical profiles. The laser-based methods provide rapid chemical profiling and micro-spatial information of gunshot residue particles, with minimal destruction of the sample and high accuracy. Chemical mapping of 25 micro-regions per sample is possible in 2-10 minutes by LIBS and LA-ICP-MS, offering new tools for more comprehensive forensic case management and quick GSR screening in environmental and occupational sciences.

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

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.

Development of tailor-made inorganic gunshot residue (IGSR) microparticle standards and characterization with a multi-technique approach.

The forensic analysis of inorganic gunshot residues (IGSR) involves analytical measurements from samples taken from skin and other substrates. The standard practice for IGSR analysis recommends the use of Scanning Electron Microscopy-Energy Dispersive X-Ray Spectroscopy (SEM-EDS) to identify the gunshot residues using combined information of the particle's morphology and elemental composition. However, the current deficit on IGSR standard reference materials (SRM) limits the optimization of SEM-EDS for modern, lead-free ammunition and the development of emerging analytical techniques. This study aims to enhance existing capabilities by producing tailor-made microparticle suspensions that can be used for the quality control of GSR analysis, validation of existing and emerging methods, interlaboratory testing, and systematic transfer and persistence studies. To fill this gap, IGSR microparticle standards were developed by discharging various leaded and lead-free primers under controlled conditions and creating suspensions in an organic medium, then evaluated for homogeneity and stability of morphology and elemental composition. The IGSR microparticles suspensions were evaluated by three analytical techniques-SEM-EDS, Laser-Induced Breakdown Spectroscopy (LIBS) and Inductively Coupled Plasma-Mass Spectrometry (ICP-MS) -to characterize the elemental composition and particle morphology. The ICP-MS digestion method was validated for these novel IGSR microparticle suspensions, and figures of merit and ruggedness testing are reported. The standard demonstrated stability in its dry and suspension forms, providing versatility for use in multiple types of analytical methods and substrates. This research is anticipated to assist forensic and environmental scientists by providing IGSR standards that can strengthen research, expand access to new detection techniques, and enhance laboratories' cross-validation and quality assurance.