Voltammetric analysis of luminescent markers in gunshot residues

Currently, SEM‐EDS is used to detect gunshot residue (GSR) from the presence of Ba, Pb, and Sb in the sample. However, the development of new nontoxic ammunition (NTA) has prevented conventional metals from being found. In this work, we aim to determine the presence of an inorganic luminescent chemical marker based on rare earth in gunshot residues using the technique of squarewave voltammetry (SWV). After firing, the luminescent complex [(Eu2Zr)(btc)3(Hbtc)0.5.6H2O], which is used as a chemical marker, can be detected under a UV lamp. An aqueous solution with 0.1 mol L−1 KCl as supporting electrolyte can be easily collected on carbon paste electrode surfaces for SWV analysis A = 100 mV, f = 10 Hz, and step potential of 5 mV are required. The luminescent marker incorporated into the carbon paste electrode showed two anodic peak currents in the region of 0.4 V (vs Ag/AgCl) and at 0.75 V (vs Ag/AgCl) and also a cathodic one in 0.4 V (vs Ag/AgCl). SEM‐EDS was able to analyze the same voltammetric results for conventional and nontoxic ammunition containing the luminescent marker. Therefore, voltammetry and SEM‐EDS are valid for detecting the new residue marker in GSR. Despite this, the electrochemical method is still more advantageous because of its low cost and lack of expensive equipment and supplies in forensic laboratories.

[1]  Marcelo F de Oliveira,et al.  Synthesis and Structural Characterization of an Amorphous and Photoluminescent Mixed Eu/Zr Coordination Compound, a Potential Marker for Gunshot Residues , 2022, Sci.

[2]  Luis E. Arroyo,et al.  Comparison of portable and benchtop electrochemical instruments for detection of inorganic and organic gunshot residues in authentic shooter samples , 2022, Journal of forensic sciences.

[3]  Osnat Israelsohn,et al.  Finding GSR evidence on used towels. , 2021, Forensic science international.

[4]  Kriti Nigam,et al.  Trends in Gunshot Residue Detection by Electrochemical Methods for Forensic Purpose , 2021, Journal of Analysis and Testing.

[5]  C. Hussain,et al.  Sensors for the Detection of Explosives and Gunshots Residues , 2020 .

[6]  M. Lucena,et al.  Luminescent Marker for GSR: Evaluation of the Acute Oral and Inhalation Toxicity of the MOF [Eu(DPA)(HDPA)]. , 2020, ACS applied bio materials.

[7]  K. Kirkbride,et al.  Gunshot residue background on police officers: Considerations for secondary transfer in GSR evidence evaluation. , 2019, Forensic science international.

[8]  Alicia Doña-Fernández,et al.  Real-time detection of GSR particles from crime scene: A comparative study of SEM/EDX and portable LIBS system. , 2018, Forensic science international.

[9]  Luis E. Arroyo,et al.  Fast identification of inorganic and organic gunshot residues by LIBS and electrochemical methods , 2018 .

[10]  C. García-Ruiz,et al.  Investigation of the use of luminescent markers as gunshot residue indicators. , 2017, Forensic science international.

[11]  J. Yun,et al.  Redox behaviors of zirconium in molten LiCl-KCl eutectic salt based on the comproportionation reaction between Zr(0) and Zr(IV) , 2017 .

[12]  R. Silva,et al.  DETERMINAÇÃO RÁPIDA E SIMPLES DE CITRATO DE SILDENAFILA (VIAGRA® E GENÉRICOS) EMPREGANDO ELETRODO IMPRESSO DE CARBONO EM SISTEMAS FIA E BIA COM DETECÇÃO AMPEROMÉTRICA , 2017 .

[13]  C. Banks,et al.  An Introduction to Forensic Electrochemistry , 2016 .

[14]  Jan Halámek,et al.  Forensic Science: Multidisciplinary Approach, A , 2015 .

[15]  N. Aristov,et al.  Cyclic Voltammetry - A Versatile Electrochemical Method Investigating Electron Transfer Processes , 2015 .

[16]  M A M Lucena,et al.  Use of luminescent gunshot residues markers in forensic context. , 2014, Forensic science international.

[17]  F. S. Semaan,et al.  Voltametrias: Uma Breve Revisão Sobre os Conceitos , 2013 .

[18]  Joseph Wang,et al.  Electrochemical Detection of Gunshot Residue for Forensic Analysis: A Review , 2013 .

[19]  R. Compton,et al.  Electrochemistry of Zirconium Tetrachloride in the Ionic Liquid N‐Butyl‐N‐methylpyrrolidinium Bis(trifluoromethylsulfonyl)imide: Formation of Zr(III) and Exploitation of ZrCl4 as a Facile Ionic Liquid Drying Agent , 2012 .

[20]  E. Kılıç,et al.  Simultaneous Determination of Antimony and Lead in Gunshot Residue by Cathodic Adsorptive Stripping Voltammetric Methods , 2011 .

[21]  M. O. Rodrigues,et al.  High photoluminescent metal-organic frameworks as optical markers for the identification of gunshot residues. , 2011, Analytical chemistry.

[22]  A. Pinto,et al.  SEM/EDS analysis and characterization of gunshot residues from Brazilian lead-free ammunition. , 2008, Forensic science international.

[23]  M. D. Rooij,et al.  Electrochemical Methods: Fundamentals and Applications , 2003 .

[24]  H. Dewald,et al.  Differential pulse anodic stripping voltammetry of barium and lead in gunshot residues. , 2001, Forensic science international.

[25]  H. Dewald,et al.  Differential pulse anodic stripping voltammetry of lead and antimony in gunshot residues , 1999 .

[26]  C. Brihaye,et al.  Gunpowder residues detection by anodic stripping voltammetry , 1982 .

[27]  O. Serra,et al.  TERRAS RARAS: TABELA PERIÓDICA, DESCOBRIMENTO, EXPLORAÇÃO NO BRASIL E APLICAÇÕES , 2019, Química Nova.

[28]  O. Serra,et al.  Terras raras no Brasil: histórico, produção e perspectivas , 2014 .