The Capability of Raman Microspectroscopy to Differentiate Printing Inks
Chelsea E. Johnson M.S.
Hertzberg-Davis Forensic Science Center, School of Criminal Justice and Criminalistics, California State University, Los Angeles, 1800 Paseo Rancho Castilla, Los Angeles, CA, 90032
Search for more papers by this authorPaul Martin Ph.D.
CRAIC Technologies, 948 N. Amelia Ave., San Dimas, CA, 91773
Search for more papers by this authorCorresponding Author
Katherine A. Roberts Ph.D.
Hertzberg-Davis Forensic Science Center, School of Criminal Justice and Criminalistics, California State University, Los Angeles, 1800 Paseo Rancho Castilla, Los Angeles, CA, 90032
Additional information and reprint requests:.
Katherine A. Roberts, Ph.D.
Hertzberg-Davis Forensic Science Center
School of Criminal Justice and Criminalistics
California State University, Los Angeles
1800 Paseo Rancho Castilla
Los Angeles, CA 90032
E-mail: [email protected]
Search for more papers by this authorTatiana Trejos Ph.D.
Department of Chemistry and Biochemistry and International Forensic Research Institute, Florida International University, Modesto A. Maidique Campus, OE 116A, Miami, FL, 33199
Search for more papers by this authorRuthmara Corzo B.S.
Department of Chemistry and Biochemistry and International Forensic Research Institute, Florida International University, Modesto A. Maidique Campus, OE 116A, Miami, FL, 33199
Search for more papers by this authorJose R. Almirall Ph.D.
Department of Chemistry and Biochemistry and International Forensic Research Institute, Florida International University, Modesto A. Maidique Campus, OE 116A, Miami, FL, 33199
Search for more papers by this authorAlan M. Safer Ph.D.
Department of Mathematics and Statistics, California State University, Long Beach, 1250 Bellflower Blvd., Long Beach, CA, 90840
Search for more papers by this authorChelsea E. Johnson M.S.
Hertzberg-Davis Forensic Science Center, School of Criminal Justice and Criminalistics, California State University, Los Angeles, 1800 Paseo Rancho Castilla, Los Angeles, CA, 90032
Search for more papers by this authorPaul Martin Ph.D.
CRAIC Technologies, 948 N. Amelia Ave., San Dimas, CA, 91773
Search for more papers by this authorCorresponding Author
Katherine A. Roberts Ph.D.
Hertzberg-Davis Forensic Science Center, School of Criminal Justice and Criminalistics, California State University, Los Angeles, 1800 Paseo Rancho Castilla, Los Angeles, CA, 90032
Additional information and reprint requests:.
Katherine A. Roberts, Ph.D.
Hertzberg-Davis Forensic Science Center
School of Criminal Justice and Criminalistics
California State University, Los Angeles
1800 Paseo Rancho Castilla
Los Angeles, CA 90032
E-mail: [email protected]
Search for more papers by this authorTatiana Trejos Ph.D.
Department of Chemistry and Biochemistry and International Forensic Research Institute, Florida International University, Modesto A. Maidique Campus, OE 116A, Miami, FL, 33199
Search for more papers by this authorRuthmara Corzo B.S.
Department of Chemistry and Biochemistry and International Forensic Research Institute, Florida International University, Modesto A. Maidique Campus, OE 116A, Miami, FL, 33199
Search for more papers by this authorJose R. Almirall Ph.D.
Department of Chemistry and Biochemistry and International Forensic Research Institute, Florida International University, Modesto A. Maidique Campus, OE 116A, Miami, FL, 33199
Search for more papers by this authorAlan M. Safer Ph.D.
Department of Mathematics and Statistics, California State University, Long Beach, 1250 Bellflower Blvd., Long Beach, CA, 90840
Search for more papers by this authorAbstract
This study applies Raman microspectroscopy to differentiate the chemical components in printing inks of different brands, colors, and type using the 532 nm and 785 nm excitation wavelengths. Spectra were collected from 319 inks (78 inkjet, 76 toner, 79 offset, and 86 intaglio) representing various colors. Comparisons were performed to calculate discrimination capability percentages for each ink type. Overall, Raman microspectroscopy differentiates according to the following hierarchy: intaglio (96%), inkjet (92%), offset (90%), and toner (61%). The ability of Raman microspectroscopy to differentiate between same-colored inks from different brands was dependent on the color and ink analyzed. Based on ink color, the discrimination capability ranged from 75 to 94% (inkjet), 0 to 86% (toner), and 0 to 77% (offset). Copper phthalocyanine was detected in cyan inks and various intaglio inks, while carbon black was identified in black inkjet, offset, and intaglio inks.
References
- 1Papson K, Stachura S, Boralsky L, Allison J. Identification of colorants in pigmented pen inks by laser desorption mass spectrometry. J Forensic Sci 2008; 53(1): 100–6.
- 2Houlgrave S, LaPorte GM, Stephens JC, Wilson JL. The classification of inkjet inks using AccuTOF DART (Direct Analysis in Real Time) mass spectrometry – a preliminary study. J Forensic Sci 2013; 58(3): 813–21.
- 3Donnelly S, Marrero JE, Cornell T, Fowler K, Allison J. Analysis of pigmented inkjet printer inks and printed documents by laser desorption/mass spectrometry. J Forensic Sci 2010; 55(1): 129–35.
- 4Jones RW, Cody RB, McClelland JF. Differentiating writing inks using direct analysis in real time mass spectrometry. J Forensic Sci 2006; 51(4): 915–8.
- 5Jones RW, McClelland JF. Analysis of writing inks on paper using direct analysis in real time mass spectrometry. Forensic Sci Int 2013; 231(1–3): 73–81.
- 6Heudt L, Debois D, Zimmerman TA, Köhler L, Fouzia B, Partouche F, et al. Raman spectroscopy and laser desorption mass spectrometry for minimal destructive forensic analysis of black and color inkjet printed documents. Forensic Sci Int 2012; 219(1–3): 64–75.
- 7Trejos T, Corzo R, Subedi K, Almirall J. Characterization of toners and inkjets by laser ablation spectrochemical methods and scanning electron microscopy-energy dispersive X-ray spectroscopy. Spectrochim Acta B 2014; 92: 9–22.
- 8Egan WJ, Galipo RC, Kochanowski BK, Morgan SL, Bartick EG, Miller ML, et al. Forensic discrimination of photocopy and printer toners. III. Multivariate statistics applied to scanning electron microscopy and pyrolysis gas chromatography/mass spectrometry. Anal Bioanal Chem 2003; 376(8): 1286–97.
- 9Hoehse M, Paul A, Gornushkin I, Panne U. Multivariate classification of pigments and inks using combined Raman spectroscopy and LIBS. Anal Bioanal Chem 2012; 402: 1443–50.
- 10Chaplin TD, Clark RJ, Jacobs D, Jensen K, Smith GD. The Gutenberg Bibles: analysis of the illuminations and inks using Raman spectroscopy. Anal Chem 2005; 77(11): 3611–22.
- 11Kivioja A, Hartus T, Vuorinen T, Gane P, Jääskeläinen AS. Use of total internal reflection Raman (TIR) and attenuated total reflection infrared (ATR-IR) spectroscopy to analyze component separation in thin offset ink films after setting on coated paper surfaces. Appl Spectrosc 2013; 67(6): 661–71.
- 12Vikman K, Sipi K. Applicability of FTIR and Raman spectroscopic methods to the study of paper-ink interactions in digital prints. J Imaging Sci Technol 2003; 47(2): 139–48.
- 13Braz A, Lopez-Lopez M, Garcia-Ruiz C. Raman spectroscopy for forensic analysis of inks in questioned documents. Forensic Sci Int 2013; 232(1–3): 206–12.
- 14Krol M, Karoly A, Koscielniak P. Raman spectroscopy and capillary electrophoresis applied to forensic colour inkjet printer inks analysis. Forensic Sci Int 2014; 242: 142–9.
- 15Zieba-Palus J, Kunicki M. Application of the micro-FTIR spectroscopy, Raman spectroscopy and XRF method examination of inks. Forensic Sci Int 2006; 158(2–3): 164–72.
- 16Claybourn M, Ansell M. Using Raman spectroscopy to solve crime: inks, questioned documents and fraud. Sci Justice 2000; 40(4): 261–71.
- 17Braz A, Lopez-Lopez M, Montalvo G, Garcia-Ruiz C. Forensic discrimination of inkjet-printed lines by Raman spectroscopy and surface-enhanced Raman spectroscopy. Aust J Forensic Sci 2015; 47(4): 411–20.
- 18Udriştioiu EG, Bunaciu AA, Aboul-Enein HY, Tănase IG. Forensic analysis of color toners by Raman spectroscopy. Instrum Sci Technol 2009; 37: 23–9.
- 19Bell S, Stewart S, Ho YC, Craythorne B, Speers S. Comparison of the discriminating power of Raman and surface-enhanced Raman spectroscopy with established techniques for the examination of liquid and gel inks. J Raman Spect 2013; 44: 509–17.
- 20Merrill R, Bartick E, Mazzella W. Studies of techniques for analysis of photocopy toners by IR. J Forensic Sci 1996; 41(2): 264–71.
- 21Merrill RA, Bartick EG, Taylor JH III. Forensic discrimination of photocopy and printer toners I. The development of an infrared spectral library. Anal Bioanal Chem 2003; 376(8): 1272–8.
- 22Assis AC, Barbosa MF, Nabais JM, Custódio AF, Tropecelo P. Diamond cell Fourier transform infrared spectroscopy transmittance analysis of black toners on questioned documents. Forensic Sci Int 2012; 214(1–3): 59–66.
- 23Williamson R, Raeva A, Almirall JR. Characterization of printing inks using DART-Q-TOF-MS and attenuated total reflectance (ATR) FTIR. J Forensic Sci 2016; 61(3): 706–14.
- 24Corzo R, Subedi K, Trejos T, Almirall JR. Evaluation of the forensic utility of scanning electron microscopy-energy dispersive spectroscopy and laser ablation-inductively coupled plasma-mass spectrometry for printing ink examinations. J Forensic Sci 2016; 61(3): 725–34.
- 25Trejos T, Torrione P, Corzo R, Raeva A, Subedi K, Williamson R, et al. A novel forensic tool for the characterization and comparison of printing ink evidence: development and evaluation of a searchable database using data fusion of spectrochemical methods. J Forensic Sci 2016; 61(3): 715–24.
- 26http://www.imaging.org/ist/resources/tutorials/inkjet_printer.cfm (accessed December 30, 2013).
- 27Leach RH. The printing ink manual, 5th edn. Dordrecht, the Netherlands: Springer, 1993.
10.1007/978-1-4020-6187-5 Google Scholar
- 28Božičević MS, Gajović A, Zjakić I. Identifying a common origin of toner printed counterfeit banknotes by micro-Raman spectroscopy. Forensic Sci Int 2012; 223(1–3): 314–20.
- 29de Almeida MR, Correa DN, Rocha WFC, Scafi FJO, Poppi RJ. Discrimination between authentic and counterfeit banknotes using Raman spectroscopy and PLS-DA with uncertainty estimation. Microchem J 2013; 109: 170–7.
- 30Palenik CS, Palenik S, Herb J, Groves E. Fundamentals of forensic pigment identification by Raman microspectroscopy: a practical identification guide and spectral library for forensic science laboratories. Elgin, IL: National Institute of Justice, Office of Justice Programs, U.S. Department of Justice, 2011; Report No.: 2010-DN-BX-K.
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