Analytical and Bioanalytical Chemistry

, Volume 408, Issue 18, pp 4965–4973 | Cite as

Surface-enhanced Raman spectroscopy for the analysis of smokeless gunpowders and macroscopic gunshot residues

  • María López-López
  • Virginia Merk
  • Carmen García-Ruiz
  • Janina Kneipp
Research Paper


Gunshot residues (GSR) result from the discharge of a firearm being a potential piece of evidence in criminal investigations. The macroscopic GSR particles are basically formed by burned and non-burned gunpowder. Motivated by the demand of trace analysis of these samples, in this paper, the use of surface-enhanced Raman scattering (SERS) was evaluated for the analysis of gunpowders and macroscopic GSR particles. Twenty-one different smokeless gunpowders were extracted with ethanol. SERS spectra were obtained from the diluted extracts using gold nanoaggregates and an excitation wavelength of 633 nm. They show mainly bands that could be assigned to the stabilizers diphenylamine and ethylcentralite present in the gunpowders. Then, macroscopic GSR particles obtained after firing two different ammunition cartridges on clothing were also measured using the same procedure. SERS allowed the detection of the particles collected with an aluminum stub from cloth targets without interferences from the adhesive carbon. The results demonstrate the great potential of SERS for the analysis of macroscopic GSR particles. Furthermore, they indicate that the grain-to-grain inhomogeneity of the gunpowders needs to be considered.

Graphical Abstract

SERS allows the detection of GSR particles collected with adhesive stubs from cloth targets using gold nanoaggregates and an excitation wavelength of 633 nm


Diphenylamine Forensic Gunpowder Gunshot residue SERS 



V.M. and J.K. would like to acknowledge the support by ERC Starting Grant 259432. M. López-López and C. García-Ruiz thank the European Commission for the Project HOME/2011/ISEC/AG/4000002480 accomplished with the financial support of the Prevention of and Fight against Crime Programme European Commission—Directorate—General Home Affairs. This project has been funded with the support from the European Commission. This publication reflects the views of the author, and the European Commission cannot be held responsible for any use which may be made of the information contained therein. M. López-López thanks the Spanish Ministry of Education, Culture and Sports for the José Castillejo mobility grant. V.M. acknowledges the support by the project DFG GSC 1013 (SALSA).

Compliance with ethical standards

Conflict of interest

The authors declare that they have no conflict of interest.

This chapter does not contain any studies with human participants or animals performed by any of the authors.


  1. 1.
    Scherperel G, Reid GE, Smith RW. Characterization of smokeless powders using nanoelectrospray ionization mass spectrometry (nESI-MS). Anal Bioanal Chem. 2009;294:2019–28.CrossRefGoogle Scholar
  2. 2.
    West C, Baron G, Minet JJ. Detection of gunpowder stabilizers with ion mobility spectrometry. Forensic Sci Int. 2007;166:91–101.CrossRefGoogle Scholar
  3. 3.
    López-López M, Bravo JC, García-Ruiz C, Torre M. Diphenylamine and derivatives as predictors of gunpowder age by means of HPLC and statistical models. Talanta. 2013;103:214–20.CrossRefGoogle Scholar
  4. 4.
    López-López M, Fernández MA, Sáiz J, Ferrando JL, Vega A, Torre M, et al. New protocol for the isolation of nitrocellulose from gunpowders: utility in their identification. Talanta. 2010;81:1742–9.CrossRefGoogle Scholar
  5. 5.
    Espinoza EO’N, Thornton JI. Characterization of smokeless gunpowder by means of diphenylamine stabilizer and its nitrated derivatives. Anal Chim Acta. 1994;288:57–69.CrossRefGoogle Scholar
  6. 6.
    Pérez A, Tascón ML, Vázquez MD, Batanero PS. Polarographic study on the evolution of the diphenylamine as stabiliser of the solid propellants. Talanta. 2004;62:165–73.CrossRefGoogle Scholar
  7. 7.
    MacCrehan WA, Bedner M. Development of a smokeless powder reference material for propellant and explosives analysis. Forensic Sci Int. 2006;163:119–24.CrossRefGoogle Scholar
  8. 8.
    Mathis JA, McCord BR. Gradient reversed-phase liquid chromatographic-electrospray ionization mass spectrometric method for the comparison of smokeless powders. J Chromatogr A. 2003;988:107–16.CrossRefGoogle Scholar
  9. 9.
    Joshi M, Rigsby K, Almirall JR. Analysis of the headspace composition of smokeless powders using GC-MS, GC-μECD and ion mobility spectrometry. Forensic Sci Int. 2011;208:29–36.CrossRefGoogle Scholar
  10. 10.
    Sharma SP, Lahiri SC. A preliminary investigation into the use of FTIR microscopy as a probe for the identification of bullet entrance holes and the distance of firing. Sci Justice. 2009;49:197–204.CrossRefGoogle Scholar
  11. 11.
    de Perre C, Corbin I, Blas M, McCord BR. Separation and identification of smokeless gunpowder additives by capillary electrochromatography. J Chromatogr A. 2012;1267:259–65.CrossRefGoogle Scholar
  12. 12.
    Joshi M, Delgado Y, Guerra P, Lai H, Almirall JR. Detection of odor signatures of smokeless powders using solid phase microextraction coupled to an ion mobility spectrometer. Forensic Sci Int. 2009;188:112–8.CrossRefGoogle Scholar
  13. 13.
    Perez JJ, Flanigan PM, Brady JJ, Levis RJ. Classification of smokeless powders using laser electrospray mass spectrometry and offline multivariate statistical analysis. Anal Chem. 2013;85:296–302.CrossRefGoogle Scholar
  14. 14.
    López-López M, Delgado JJ, García-Ruiz C. Analysis of macroscopic gunshot residues by Raman spectroscopy to assess the weapon memory effect. Forensic Sci Int. 2013;231:1–5.CrossRefGoogle Scholar
  15. 15.
    López-López M, Delgado JJ, García-Ruiz C. Ammunition identification by means of the organic analysis of gunshot residues using Raman spectroscopy. Anal Chem. 2012;84:3581–5.CrossRefGoogle Scholar
  16. 16.
    Bueno J, Sikirzhytski V, Lednev I. Raman spectroscopic analysis of gunshot residue offering great potential for caliber differentiation. Anal Chem. 2012;84:4334–9.CrossRefGoogle Scholar
  17. 17.
    Bueno J, Lednev IK. Advanced statistical analysis and discrimination of gunshot residue implementing combined Raman and FT-IR Data. Anal Methods. 2013;5:6292–6.CrossRefGoogle Scholar
  18. 18.
    Bueno J, Lednev IK. Attenuated total reflectance-FT-IR imaging for rapid and automated detection of gunshot residue. Anal Chem. 2014;86:3389–96.CrossRefGoogle Scholar
  19. 19.
    Bueno J, Lednev IK. Raman microspectroscopic chemical mapping and chemometric classification for the identification of gunshot residue on adhesive tape. Anal Bioanal Chem. 2014;406:4595–9.CrossRefGoogle Scholar
  20. 20.
    López-López M, Fernández MA, García-Ruiz C. Fast analysis of complete macroscopic gunshot residues on substrates using Raman imaging. Appl Spectrosc. 2015;69:889–93.CrossRefGoogle Scholar
  21. 21.
    Brozek-Mucha Z. Comparison of cartridge case and airborne GSR—a study of the elemental composition and morphology by means of SEM-EDX. X-Ray Spectrom. 2007;36:398–407.CrossRefGoogle Scholar
  22. 22.
    Kneipp K, Kneipp H, Kneipp J. Surface-enhanced Raman scattering in local optical fields of silver and gold nanoaggregates—from single-molecule Raman spectroscopy to ultrasensitive probing in live cells. Acc Chem Res. 2006;39:443–50.CrossRefGoogle Scholar
  23. 23.
    Graham D, Goodacre R. Chemical and bioanalytical applications of surface enhanced Raman scattering spectroscopy. Chem Soc Rev. 2008;37:883–4.CrossRefGoogle Scholar
  24. 24.
    Kneipp K, Wang Y, Kneipp H, Perelman LT, Itzkan I, Dasari RR, et al. Single molecule detection using surface-enhanced Raman scattering (SERS). Phys Rev Lett. 1997;78:1667–70.CrossRefGoogle Scholar
  25. 25.
    Nie SM, Emory SR. Probing single molecules and single nanoparticles by surface-enhanced Raman scattering. Science. 1997;275:1102–6.CrossRefGoogle Scholar
  26. 26.
    López-López M, García-Ruiz C. Infrared and Raman spectroscopy techniques applied to identification of explosives. Trends Anal Chem. 2014;54:36–44.CrossRefGoogle Scholar
  27. 27.
    Hakonen A, Andersson PO, Schmidt MS, Rindzevicius T, Käll M. Explosive and chemical threat detection by surface-enhanced Raman scattering: a review. Anal Chim Acta. 2015;893:1–13.CrossRefGoogle Scholar
  28. 28.
    Tkachenko A, Xie H, Franzen S, Feldheim DL. Assembly and characterization of biomolecule-gold nanoparticle conjugates and their use in intracellular imaging. Methods Mol Biol. 2005;303:85–99.Google Scholar
  29. 29.
    López-López M, Ferrando JL, García-Ruiz C. Comparative analysis of smokeless gunpowders by Fourier transform infrared and Raman spectroscopy. Anal Chim Acta. 2012;717:92–9.CrossRefGoogle Scholar
  30. 30.
    Michota A, Bukowska J. Surface-enhanced Raman scattering (SERS) of 4-mercaptobenzoic acid on silver and gold substrates. J Raman Spectrosc. 2003;34:21–5.CrossRefGoogle Scholar
  31. 31.
    Cañamares MV, García-Ramos JV, Domingo C. Surface-enhanced Raman scattering study of the adsorption of the anthraquinone pigment alizarin on Ag nanoparticles. J Raman Spectrosc. 2004;35:921–7.CrossRefGoogle Scholar
  32. 32.
    Creighton JA. Surface Raman electromagnetic enhancement factors for molecules at the surface of small isolated metal spheres: The determination of adsorbate orientation from SERS relative intensities. Surf Sci. 1983;124:209–19.CrossRefGoogle Scholar
  33. 33.
    Khaing MK, Chang CF, Sun Y, Fan X. Rapid, sensitive DNT vapor detection with UV-assisted photo-chemically synthesized gold nanoparticle SERS substrates. Analyst. 2011;136:2811–7.CrossRefGoogle Scholar
  34. 34.
    Gong Z, Du H, Cheng F, Wang C, Wang C, Fan M. Fabrication of SERS swab for direct detection of trace explosives in fingerprints. ACS Appl Mater Interfaces. 2014;6:21931–7.CrossRefGoogle Scholar
  35. 35.
    Sylvia JM, Janni JA, Klein JD, Spencer KM. Surface-enhanced Raman detection of 2,4-dinitrotoluene impurity vapor as a marker to locate landmines. Anal Chem. 2000;72:5834–40.CrossRefGoogle Scholar
  36. 36.
    Corrigan DS, Weaver MJ. Coverage-dependent orientation of adsorbates as probed by potential-difference infrared spectroscopy: azide, cyanate, and thiocyanate at silver electrodes. J Phys Chem. 1986;90:5300–6.CrossRefGoogle Scholar
  37. 37.
    Moskovits M, DiLella DP, Maynard KJ. Surface Raman spectroscopy of a number of cyclic aromatic molecules adsorbed on silver: selection rules and molecular reorientation. Langmuir. 1988;4:67–76.CrossRefGoogle Scholar

Copyright information

© Springer-Verlag Berlin Heidelberg 2016

Authors and Affiliations

  • María López-López
    • 1
    • 2
  • Virginia Merk
    • 3
  • Carmen García-Ruiz
    • 1
    • 2
  • Janina Kneipp
    • 3
  1. 1.Department of Analytical Chemistry, Physical Chemistry and Chemical EngineeringUniversity of AlcaláAlcalá de HenaresSpain
  2. 2.University Institute of Research in Police Sciences, Edificio Polivalente de QuímicaUniversity of AlcaláAlcalá de HenaresSpain
  3. 3.Department of ChemistryHumboldt-Universität zu BerlinAdlershofGermany

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