Our research group previously reported a novel method for the detection of gunshot residue (GSR) via tape lifting combined with Raman microspectroscopic mapping and multivariate analysis. This initial study achieved proof of concept for this approach. Here, we report validation studies which investigate the reproducibility/ruggedness and specificity of the approach. Raman mapping for GSR detection on adhesive tape was performed on an independent Raman microscope, not used to generate the training set. These independent spectra were classified against the original training dataset using support vector machine discriminant analysis (SVM-DA). The resulting classification rates of 100% illustrate the reproducibility of the technique, its independence upon a specific instrument and provide an external validation for the approach. Additionally, the same procedure for GSR collection (tape lifting) was performed to collect samples from environmental sources, which could potentially provide false-positive assignments for current GSR analysis techniques. Thus, particles associated with automotive mechanics were collected. Automotive brake and tire materials are often composed of the heavy metals lead, barium, and antimony, which are the key elements targeted by current GSR detection technique. It was determined that Raman spectroscopic analysis was not susceptible to misclassifications from these samples. Results from these validation experiments illustrate the great potential of Raman microspectroscopic mapping used with tape lifting as a viable complimentary tool to current methodologies for GSR detection. Furthermore, current methodologies are not well-developed for automated organic GSR detection. Illustrated here, Raman microscoptrosocpic mapping has the potential for the automatic identification of organic GSR.
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López-López M, García-Ruiz C. Recent non-chemical approaches to estimate the shooting distance. Forensic Sci Int. 2014;239:79–85. https://doi.org/10.1016/j.forsciint.2014.03.023.
American Society for Testing and Materials. Standard guide for gunshot residue analysis by scanning electron microscopy/energy dispersive X-ray spectrometry. West Conshohocken: ASTM International; 2010.
Scientific Working Group for Gunshot Residue. Guide for Primer Gunshot Residue Analysis by Scanning Electron Microscopy/Energy Dispersive X-Ray Spectrometry, 2011.
Brożek-Mucha Z. Trends in analysis of gunshot residue for forensic purposes. Anal Bioanal Chem. 2017;409(25):5803–11. https://doi.org/10.1007/s00216-017-0460-1.
Nesbitt RS, Wessel JE, Jones PF. Detection of gunshot residue by use of the scanning electron microscope. J Forensic Sci. 1976;21(3):595–610.
Ricci C, Chan KLA, Kazarian SG. Combining the tape-lift method and Fourier transform infrared spectroscopic imaging for forensic applications. Appl Spectrosc. 2006;60(9):1013–21.
Widjaja E. Latent fingerprints analysis using tape-lift, Raman microscopy, and multivariate data analysis methods. Analyst. 2009;134(4):769–75. https://doi.org/10.1039/b808259f.
Bueno J, Lednev IK. Attenuated total reflectance-FT-IR imaging for rapid and automated detection of gunshot residue. Anal Chem. 2014;86(7):3389–96. https://doi.org/10.1021/ac4036718.
West MJ, Went MJ. The spectroscopic detection of exogenous material in fingerprints after development with powders and recovery with adhesive lifters. Forensic Sci Int. 2008;174(1):1–5. https://doi.org/10.1016/j.forsciint.2007.02.026.
Doty KC, Lednev IK. Raman spectroscopy for forensic purposes: recent applications for serology and gunshot residue analysis. TrAC. 2018;103:215–22.
Khandasammy SR, Fikiet MA, Mistek E, Ahmed Y, Halámková L, Bueno J, et al. Bloodstains, Paintings, and drugs: Raman spectroscopy applications in forensic science. Forensic Chem. 2018;8:111–33. https://doi.org/10.1016/j.forc.2018.02.002.
Bueno J, Lednev IK. Raman microspectroscopic chemical mapping and chemometric classification for the identification of gunshot residue on adhesive tape. Anal Bioanal Chem. 2014;406(19):4595–9.
Garofano L, Capra M, Ferrari F, Bizzaro GP, Di Tullio D, Dell'Olio M, et al. Gunshot residue - further studies on particles of environmental and occupational origin. Forensic Sci Int. 1999;103(1):1–21.
Wolten GM, Nesbitt RS, Calloway AR, Loper GL. Particle analysis for the detection of gunshot residue. 2: occupational and environmental particles. J Forensic Sci. 1979;24(2):423–30.
Cardinetti B, Ciampini C, D'Onofrio C, Orlando G, Gravina L, Ferrari F, et al. X-ray mapping technique: a preliminary study in discriminating gunshot residue particles from aggregates of environmental occupational origin. Forensic Sci Int. 2004;143(1):1–19.
Torre C, Mattutino G, Vasino V, Robino C. Brake linings: a source of non-GSR particles containing lead, barium, and antimony. J Forensic Sci. 2002;47(3):494–504.
Dalby O, Butler D, Birkett JW. Analysis of gunshot residue and associated materials—a review. J Forensic Sci. 2010;55(4):924–43.
Bueno J, Sikirzhytski V, Lednev IK. Raman spectroscopic analysis of gunshot residue offering great potential for caliber differentiation. Anal Chem. 2012;84(10):4334–9. https://doi.org/10.1021/ac203429x.
Wise BM, Gallagher NB, Bro R, Shaver JM, Windig W, Koch RS. PLS Toolbox 3.5 for use with MATLABTM. Eigenvector Research, Inc., Manson, 2004.
Hofmann T, Scholkopf B, Smola AJ. Kernel methods in machine learning. Ann Stat. 2008;36(3):1171–220. https://doi.org/10.1214/009053607000000677.
Tuinstra F, Koenig JL. Raman spectrum of graphite. J Chem Phys. 1970;53(3):1126–30.
Moxnes JF, Jensen TL, Smestad E, Unneberg E, Dullum O. Lead free ammunition without toxic propellant gases. Propellants, Explos, Pyrotech. 2013;38(2):255–60.
Robin X, Turck N, Hainard A, Tiberti N, Lisacek F, Sanchez J-C, et al. pROC: an open-source package for R and S+ to analyze and compare ROC curves. BMC Bioinformatics. 2011;12(1):77. https://doi.org/10.1186/1471-2105-12-77.
Fawcett T. An introduction to ROC analysis. Pattern Recognit Lett. 2006;27(8):861–74. https://doi.org/10.1016/j.patrec.2005.10.010.
Mann CK, Vickers TJ. Instrument-to-instrument transfer of Raman spectra. Appl Spectrosc. 1999;53(7):856–61.
Foremost, we would like to thank G.R. Auto Repair Shop, Inc. in Delmar, NY, for the environmental contaminant samples. We are also grateful to Lieutenant Heller and Sergeant D’Allaird of the New York State Police for providing the GSR samples. We also thank Claire K. Muro for assistance with manuscript editing. The opinions, findings, and conclusions or recommendations expressed here are those of the authors and do not necessarily reflect those of the U.S. Department of Justice.
This work was supported by Award No. 2016-DN-BX-0166 awarded by the National Institute of Justice, Office of Justice Programs, U.S. Department of Justice.
Conflict of interest
The authors declare that they have no conflict of interest.
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Bueno, J., Halámková, L., Rzhevskii, A. et al. Raman microspectroscopic mapping as a tool for detection of gunshot residue on adhesive tape. Anal Bioanal Chem 410, 7295–7303 (2018). https://doi.org/10.1007/s00216-018-1359-1
- Raman spectroscopy
- Gunshot residue
- Chemical mapping