Sociedade Brasileira de Química (SBQ)

Área: INO

On the use of a microspectrometer for analyzing Rare Earth marked gunshot

residues
Rodrigo Galvão dos Santos (PQ)1, Jorge Fernando Silva de Menezes (PQ)2,3, Vinícius Santos de Santana (IC)2
rodrigo.galvao@pefoce.ce.gov.br; jorge_fernando@ufrb.edu.br
1
Crime Scene Investigator - Perícia Forense do Estado do Ceará, Fortaleza/CE, Brazil; 2Universidade Federal do
Recôncavo da Bahia, Amargosa/BA, Brazil; 3National Institute of Science and Technology in Energy and Environment,
Universidade Federal da Bahia, Salvador/BA, Brazil
Keywords: gunshot residues, spectroscopy, rare earth ions.

Highlights
A microspectrometer was used to analyze rare earth marked gunshot residues. The equipment allowed for fast,
contactless and non destructive assessment of the fluorescence emission at low mass concentrations (0.17% wt.).

Abstract
According to the latest official reports, there are about 4.4 million firearms in private hands in Brazil [1], which translates
to approximately 2 guns for every 100 people. On the other hand, Brazil still registers over 20 homicides for every 100
thousand people, thus being the 8th most violent country in the world. Taking into account that firearms are used in
76% of the homicides in the country, the development of new methods for forensic ballistics is of great interest,
particularly for the identification of gunshot residues (GSR) produced from firearms. In Brazil, the colorimetric test for
Pb is still commonly used. However, one of its major drawbacks is the possibility of contamination with other lead
sources, thus leading to false positive results [2,3]. In order to overcome these limitations, some techniques have been
proposed involving Rare Earth (RE) marked GSR, such as Electrospray Ionization Fourier Transform Ion Cyclotron
Resonance Mass Spectrometry (ESIFT-ICR MS) [4] and fluorescence spectroscopy with mixed Eu3+/Tb3+ frameworks].
Two RE based luminescent compounds were chosen in this study: [Tb(ACAC) 3(H2O)3] and [Eu(TTA)3(H2O)2]
(ACAC=acetylacetone, TTA=thenoyltrifluoroacetone), which give a green and red emission respectively. These
hydrated β-diketone based compounds are well known in the literature and thus can be used as benchmarks for the
technique. The materials were prepared following tried-and-true methods and a high resolution spectrometer
(microspectrophotometer) was used to investigate the luminescence emission of RE marked GSR. The
microspectrophotometer in question is a dual-video spectral comparator (Regula 4308), which is originally intended
for authenticity verification of documents. In order to assess the effectiveness of the Regula 4308 to identify RE marked
GSR, a test was conducted using ten rounds of .380 ACP ammunition (CBC company Non-Toxic Ammunition). Each
of the rounds was disassembled using an inertia bullet puller and 10 mg (0.17% wt.) of the Tb3+ compound was added
to the gunpowder of five rounds, while the same amount of Eu3+ compound was added to the remaining five. The 10
rounds were fired using two similar pistols and the ten cartridge cases were recovered for analysis. Using the
microspectrophotometer module of the Regula 4308, the ten cases can be analyzed in a single run. Under
magnification, fragments of the luminescent compounds were visible under a 365 nm excitation. A 2 s integration time
was used for the spectral acquisition and the color coordinates in the CIE 1931 color space were calculated. The
coordinates are close to the spectral locus of the CIE diagrams, as a result of the high color purity of the RE emission
spectra, particularly for the Eu3+ compound, which is still preserved after the gunpowder ignition. The results indicate
the effectiveness of a microspectrometer for rapid, contactless and non destructive analysis of RE marked GSR. The
luminescence emission was also detectable inside the gun barrels and visible to the naked eye using a portable 365
nm light source (Convoy S2+ UV flashlight), thus allowing for on-site crime scene photography. This technique can
also be used to assess new RE based markers or nanoparticles, besides being able to identify different batches of
ammunition with different color emission signatures.

Acknowledgments
The authors are grateful to the Fundação de Amparo à Pesquisa do Estado da Bahia (FAPESB) and the Conselho
Nacional de Desenvolvimento Científico e Tecnológico (INCT-Energia e Meio Ambiente) for financial support.

References
[1] Anuário Brasileiro de Segurança Pública. Year 16 (Brazil, 2022).
[2] M. R. Bartsch, H. J. Kobus, and K. P. Wainwright, J. Forensic Sci. 41, 14047J (1996).
[3] S. Charles and N. Geusens, Forensic Sci. Int. 216, 78–81 (2012).
[4] C. A. Destefani et al., Microchem. J. 116, 216–224 (2014).
46a Reunião Anual da Sociedade Brasileira de Química: "Química: Ligando ciências e neutralizando desigualdades"