Forensic applications of Raman spectroscopy for the in situ analyses of pigments and dyes in ink and paint evidence

Raman spectroscopy has proven to be a very useful tool for the forensic examination of various colored evidence, including its use in identifying pigments and dyes in paint and inks. Because both paint and inks consist of complex heterogeneous matrices, forensic scientists typically use a battery of different tests to characterize them, with each method contributing information that will be evaluated and integrated to produce an overall compositional profile. The contribution of the Raman method for the examination of these types of evidentiary materials will be described as well as the factors, which will show why this technique is suitable for the forensic endeavor. The literature offers abundant examples that show how Raman spectroscopy produces data that provide a very high degree of discrimination between samples, can perform non-destructive microscopical in situ analyses, requires minimal or no sample preparation, and produces data that can be easily stored for database purposes. In this review article, a comprehensive review of the forensic applications of Raman spectroscopy for the characterization, differentiation, comparison, and identification of trace evidence and questioned documents, consisting of paint and ink, respectively, is presented. Copyright © 2015 John Wiley & Sons, Ltd.

[1]  S. Bell,et al.  Rapid Forensic Analysis and Identification of “Lilac” Architectural Finishes Using Raman Spectroscopy , 2005, Applied spectroscopy.

[2]  R. M. Seifar,et al.  Applicability of surface-enhanced resonance Raman scattering for the direct discrimination of ballpoint pen inks. , 2001, The Analyst.

[3]  G. Massonnet,et al.  The micro Raman analysis of paint evidence in criminalistics: case studies , 2006 .

[4]  M. Fleischmann,et al.  Raman spectra of pyridine adsorbed at a silver electrode , 1974 .

[5]  B. Trzcińska,et al.  Application of Infrared and Raman Spectroscopy in Paint Trace Examination , 2013, Journal of Forensic Sciences.

[6]  Valery N. Aginsky Forensic Examination of “Slightly Soluble” Ink Pigments Using Thin-Layer Chromatography , 1993 .

[7]  E. Suzuki,et al.  Infrared Spectra of U.S. Automobile Original Topcoats (1974–1989): III. In Situ Identification of Some Organic Pigments Used in Yellow, Orange, Red, and Brown Nonmetallic and Brown Metallic Finishes—Benzimidazolones , 1997 .

[8]  Samantha Boyd,et al.  Raman spectroscopy of blood samples for forensic applications. , 2011, Forensic science international.

[9]  Nicole M Egli,et al.  Survey of crowbar and household paints in burglary cases-population studies, transfer and interpretation. , 2005, Forensic science international.

[10]  P. White In situ surface enhanced resonance Raman scattering (SERRS) spectroscopy of biro inks--long-term stability of colloid treated samples. , 2003, Science & justice : journal of the Forensic Science Society.

[11]  Cyril Muehlethaler,et al.  Raman analysis of multilayer automotive paints in forensic science: measurement variability and depth profile , 2014 .

[12]  P. C. White,et al.  SERRS Spectroscopy – a new technique for forensic science? , 2000 .

[13]  Bernard Gilbert,et al.  Raman spectroscopy and laser desorption mass spectrometry for minimal destructive forensic analysis of black and color inkjet printed documents. , 2012, Forensic science international.

[14]  Cedric Neumann,et al.  New perspectives in the use of ink evidence in forensic science: Part I. Development of a quality assurance process for forensic ink analysis by HPTLC. , 2009, Forensic science international.

[15]  Marco Leona,et al.  Microanalysis of organic pigments and glazes in polychrome works of art by surface-enhanced resonance Raman scattering , 2009, Proceedings of the National Academy of Sciences.

[16]  G Massonnet,et al.  Identification of organic pigments in coatings: applications to red automotive topcoats. Part III: Raman spectroscopy (NIR FT-Raman). , 1999 .

[17]  Cedric Neumann,et al.  New perspectives in the use of ink evidence in forensic science: Part III: Operational applications and evaluation. , 2009, Forensic science international.

[18]  Ulrich Panne,et al.  Multivariate classification of pigments and inks using combined Raman spectroscopy and LIBS , 2012, Analytical and Bioanalytical Chemistry.

[19]  Cedric Neumann,et al.  New perspectives in the use of ink evidence in forensic science Part II. Development and testing of mathematical algorithms for the automatic comparison of ink samples analysed by HPTLC. , 2009, Forensic science international.

[20]  Albert Harisovich Kuptsov,et al.  Applications of Fourier Transform Raman Spectroscopy in Forensic Science , 1994 .

[21]  E M Suzuki,et al.  In situ identification and analysis of automotive paint pigments using line segment excitation Raman spectroscopy: I. Inorganic topcoat pigments. , 2001, Journal of forensic sciences.

[22]  P. Ropret,et al.  Raman identification of yellow synthetic organic pigments in modern and contemporary paintings: reference spectra and case studies. , 2008, Spectrochimica acta. Part A, Molecular and biomolecular spectroscopy.

[23]  S. P. Stewart,et al.  Comparison of the discriminating power of Raman and surface-enhanced Raman spectroscopy with established techniques for the examination of liquid and gel inks , 2013 .

[24]  A. McKinley,et al.  In situ chemical analysis of modern organic tattooing inks and pigments by micro‐Raman spectroscopy , 2008 .

[25]  Janina Zięba-Palus,et al.  PRAXIS—combined μ-Raman and μ-XRF spectrometers in the examination of forensic samples , 2008 .

[26]  Igor Zjakić,et al.  Identifying a common origin of toner printed counterfeit banknotes by micro-Raman spectroscopy. , 2012, Forensic science international.

[27]  Robin J. H. Clark,et al.  Raman spectroscopic library of natural and synthetic pigments (pre- ≈ 1850 AD) , 1997 .

[28]  Janina Zieba-Palus,et al.  Application of the micro-FTIR spectroscopy, Raman spectroscopy and XRF method examination of inks. , 2006, Forensic science international.

[29]  Marco Leona,et al.  Application of Raman Spectroscopy and Surface‐Enhanced Raman Scattering to the Analysis of Synthetic Dyes Found in Ballpoint Pen Inks * , 2009, Journal of forensic sciences.

[30]  W. Mazzella,et al.  A study to investigate the evidential value of blue gel pen inks. , 2003, Journal of forensic sciences.

[31]  D. Meisel,et al.  Adsorption and surface-enhanced Raman of dyes on silver and gold sols , 1982 .

[32]  E. M. Suzuki,et al.  Analysis of Paint Evidence , 2012 .

[33]  E. M. Suzuki Infrared Spectra of U.S. Automobile Original Topcoats (1974–1989): I. Differentiation and Identification Based on Acrylonitrile and Ferrocyanide C≡N Stretching Absorptions , 1996 .

[34]  N L Poon,et al.  Differentiation of coloured inks of inkjet printer cartridges by thin layer chromatography and high performance liquid chromatography. , 2005, Science & justice : journal of the Forensic Science Society.

[35]  Janina Zięba-Palus,et al.  Examination of multilayer paint coats by the use of infrared, Raman and XRF spectroscopy for forensic purposes , 2006 .

[36]  Basudeb Saha,et al.  Application of Raman spectroscopy in forensic investigation of questioned documents involving stamp inks. , 2013, Science & justice : journal of the Forensic Science Society.

[37]  E. Bartick,et al.  Raman Spectroscopy in Forensic Science , 2009 .

[38]  Marco Leona,et al.  Nondestructive identification of natural and synthetic organic colorants in works of art by surface enhanced Raman scattering. , 2011, Analytical chemistry.

[39]  Nadim C Scherrer,et al.  Synthetic organic pigments of the 20th and 21st century relevant to artist's paints: Raman spectra reference collection. , 2009, Spectrochimica acta. Part A, Molecular and biomolecular spectroscopy.

[40]  E. M. Suzuki Infrared Spectra of U.S. Automobile Original Topcoats (1974–1989): II. Identification of Some Topcoat Inorganic Pigments Using an Extended Range (4000-220 cm −1 ) Fourier Transform Spectrometer , 1996 .

[41]  Dudley Creagh,et al.  Raman analysis of iron-gall inks on parchment , 2006 .

[42]  María López-López,et al.  Raman imaging for determining the sequence of blue pen ink crossings. , 2015, Forensic science international.

[43]  P. L. Kirk,et al.  The Ontogeny of Criminalistics , 1963 .

[44]  Paweł Kościelniak,et al.  Raman spectroscopy and capillary electrophoresis applied to forensic colour inkjet printer inks analysis. , 2014, Forensic science international.

[45]  A C Moffat,et al.  The calculation of discriminating power for a series of correlated attributes. , 1973, Journal - Forensic Science Society.

[46]  Characterization of Alkali Blue Pigment in Counterfeit Currency by High Performance Liquid Chromatography , 1984 .

[47]  S. Speers,et al.  Forensic examination of multilayer white paint by lateral scanning Raman spectroscopy , 2012 .

[48]  E. M. Suzuki,et al.  Infrared Spectra of U.S. Automobile Original Finishes. VII. Extended Range FT‐IR and XRF Analyses of Inorganic Pigments In Situ—Nickel Titanate and Chrome Titanate , 2006, Journal of forensic sciences.

[49]  Williams David Mazzella,et al.  Raman spectroscopy of blue gel pen inks. , 2005, Forensic science international.

[50]  Anna de Juan,et al.  Use of Raman spectroscopy and chemometrics to distinguish blue ballpoint pen inks. , 2015, Forensic science international.

[51]  J. Zieba-Palus,et al.  Establishing of Chemical Composition of Printing Ink , 2011, Journal of forensic sciences.

[52]  M. Xie,et al.  Nondestructive identification for red ink entries of seals by Raman and Fourier transform infrared spectrometry. , 2012, Spectrochimica acta. Part A, Molecular and biomolecular spectroscopy.

[53]  B. Saha,et al.  Silver nanoparticles doped agarose disk: highly sensitive surface-enhanced Raman scattering substrate for in situ analysis of ink dyes. , 2013, Forensic science international.

[54]  P. Esseiva,et al.  The application of chemometrics on Infrared and Raman spectra as a tool for the forensic analysis of paints. , 2011, Forensic science international.

[55]  Infrared Spectra of U.S. Automobile Original Topcoats (1974–1989): V. Identification of Organic Pigments Used in Red Nonmetallic and Brown Nonmetallic and Metallic Monocoats—DPP Red BO and Thioindigo Bordeaux , 1999 .

[56]  Cyril Muehlethaler,et al.  Influence of the shaking time on the forensic analysis of FTIR and Raman spectra of spray paints. , 2014, Forensic science international.

[57]  A. Lautié,et al.  The application of electronic and vibrational spectroscopic techniques to the identification of quinacridone pigments in vehicle paint systems , 2008 .

[58]  André Braz,et al.  Raman spectroscopy for forensic analysis of inks in questioned documents. , 2013, Forensic science international.

[59]  Infrared Spectra of U.S. Automobile Original Topcoats (1974–1989): VI. Identification and Analysis of Yellow Organic Automotive Paint Pigments—Isoindolinone Yellow 3R, Isoindoline Yellow, Anthrapyrimidine Yellow, and Miscellaneous Yellows , 1999 .

[60]  María López-López,et al.  Studying the variability in the Raman signature of writing pen inks. , 2014, Forensic science international.

[61]  Aleksandra Michalska,et al.  Characterization of Blue Pigments Used in Automotive Paints by Raman Spectroscopy , 2014, Journal of forensic sciences.

[62]  Filip Govaert,et al.  Forensic analysis of automotive paints by Raman spectroscopy , 2005 .

[63]  S. Bell,et al.  Forensic Analysis of Architectural Finishes Using Fourier Transform Infrared and Raman Spectroscopy, Part II: White Paint , 2005, Applied spectroscopy.

[64]  Paweł Kościelniak,et al.  Application of capillary electrophoresis to examination of color inkjet printing inks for forensic purposes. , 2011, Forensic science international.

[65]  G. Massonnet,et al.  A market study of green spray paints by Fourier transform infrared (FTIR) and Raman spectroscopy. , 2004, Science & justice : journal of the Forensic Science Society.

[66]  E. M. Suzuki,et al.  INFRARED SPECTRA OF U.S. AUTOMOBILE ORIGINAL TOPCOATS (1974-1989) : IV. IDENTIFICATION OF SOME ORGANIC PIGMENTS USED IN RED AND BROWN NONMETALLIC AND METALLIC MONOCOATS-QUINACRIDONES , 1998 .

[67]  M. Ansell,et al.  Using Raman spectroscopy to solve crime: inks, questioned documents and fraud. , 2000, Science & justice : journal of the Forensic Science Society.

[68]  W. Smith,et al.  Surface-Enhanced Resonance Raman Scattering of Black Inkjet Dyes in Solution and in Situ Printed onto Paper , 2003, Applied spectroscopy.

[69]  C. Rodger,et al.  Surface-Enhanced Resonance Raman Scattering and Near-Infrared Fourier Transform Raman Scattering as in Situ Probes of Ink Jet Dyes Printed on Paper , 2000 .