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

NCJ Number
302853
Journal
Analyst Volume: 146 Dated: September 2021 Pages: 5389-5402
Author(s)
Courtney Vander Pyl ; Claudia Martinez-Lopez; Korina Menking Hoggatt; Tatiana Trejos
Date Published
September 2021
Length
14 pages
Annotation

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).

Abstract

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 percent for LA-ICP-MS and 100 percent 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 percent sensitivity (true positive rate), while LIBS resulted in 89.2 percent 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 percent sensitivity for LA-ICP-MS and 44.4 percent for LIBS. Overall accuracies of 94.9 percent and 88.2 percent 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. (publisher abstract modified)

Date Published: September 1, 2021

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