Analyst. 2021 Aug 4. doi: 10.1039/d1an00689d. Online ahead of print.
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.
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