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Photofading of ballpoint dyes studied on paper by LDI and MALDI MS

  • Céline Weyermann
  • Dieter Kirsch
  • César Costa-Vera
  • Bernhard Spengler
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Abstract

The determination of the age of an ink entry from a questioned document is often a major problem and a controversial issue in forensic sciences. Therefore, it is important to understand the aging process of the different components found in ink. The aim of this work is to characterize the degradation processes of methyl violet and ethyl violet, two typical ballpoint dyes by using laser desorption/ionization (LDI) and matrix-assisted laser desorption/ionization (MALDI) mass spectrometry (MS), and to evaluate the possible application of the method to forensic examination of documents. The mass spectrometric methods were first tested and were found to be adequate for the purpose of this work. Moreover, it is possible to analyze the dye from a stroke directly from the paper (LDI-MS), so the sample preparation is minimized. The degradation of the dyes methyl violet and ethyl violet in strokes from a ballpoint pen was studied under laboratory conditions influenced by different factors such as light, wavelength of light, heat, and humidity. Then, strokes from the same ballpoint were aged naturally in the dark or under the influence of light over one year and then analyzed. The results show that the degradation of these dyes strongly depends on light fluence. Humidity also increases degradation, which can be explained by the basicity of the paper. The influence of heat on the degradation process was found to be rather weak. It was also observed that the dyes from the ink strokes did not show significant degradation after one year of storage in the dark. In conclusion, the storage conditions of a questioned document and the initial composition of the dyes in the ink have to be known for correct interpretation of the age of an ink entry. Measurements over longer periods of time are necessary to follow the degradation of dyes exempt from light exposure. LDI was found adequate and very useful for the analysis of ballpoint dyes directly from paper without further pretreatment.

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References

  1. 1.
    Brunelle, R. L.; Cantu, A. A. A Critical Evaluation of Current Ink Dating Techniques. J. Forensic Sci. 1987, 32(6), 1522–1536.Google Scholar
  2. 2.
    Steward L. F.; Guertin S. Current Status of Ink Age Determination; International Criminal Police Review (March/April): 1991; pp 9–13.Google Scholar
  3. 3.
    Brunelle, R. L.; Lee, H. Ink Dating—The State of the Art. J Forensic Sci. 1992, 37, 113–124.CrossRefGoogle Scholar
  4. 4.
    Hicks, T. Determination de l’age des encres—Possibilites de standardisation, Universite de Lausanne, Institut de Police Scientifique, Seminaire de 3eme annee. 1993.Google Scholar
  5. 5.
    Aginsky, V. N. Some New Ideas for Dating Ballpoint Inks—A Feasibility Study. J. Forensic Sci. 1993, 38(5), 1134–1150.Google Scholar
  6. 6.
    Cantu, A. A. A Sketch of Analytical Methods for Document Dating Part II. The Dynamic Approach: Determining Age Dependent Analytical Profiles. Int. J. Forensic Documents Examiners 1996, 2(3), 192–208.Google Scholar
  7. 7.
    Dormann, P. Les differentes techniques et la controverse sur la datation des encres, Universite de Lausanne, Institut de Police Scientifique, Seminaire de 2eme annee, 2000.Google Scholar
  8. 8.
    Brunelle, R. L.; Breedlove, C. H.; Midkiff, C. R. Determining the Relative Age of Ballpoint Inks Using a Single-Solvent Extraction Technique. J. Forensic Sci. 1987, 32(6), 1511–1521.Google Scholar
  9. 9.
    Cantu, A. A.; Prough, R. S. On the Relative Aging of Ink. J. Forensic Sci. 1987, 32, 1151–1174.CrossRefGoogle Scholar
  10. 10.
    Aginsky, V. N. Determination of the Age of Ballpoint Pen Inks by Gas and Densitometric Thin-Layer Chromatography. J. Chromatogr. A 1994, 678, 119–125.CrossRefGoogle Scholar
  11. 11.
    Aginsky, V. N. A New Version of the Internal Standard Method in Quantitative Thin Layer Chromatography. J. Planar Chromatogr. 1994, 7, 309–314.Google Scholar
  12. 12.
    Brunelle, R. L. A Sequential Multiple Approach to Determining the Relative Age of Writing Inks (TLC, Solvent Extraction and Relative Dating). Int. J. Forensic Documents Examiners 1995, 1(2), 94–98.Google Scholar
  13. 13.
    Andermann, T.; Neri, R. Solvent Extraction Techniques—Possibilities for Dating Ballpoint Pen Inks. Int. J. Forensic Documents Examiners. 1998, 4(3), 231–239.Google Scholar
  14. 14.
    Steward, L. F. Ballpoint Ink Age Determination by Volatile Component Comparison—A Preliminary Study. J. Forensic Sci. 1985, 30(2), 405–411.Google Scholar
  15. 15.
    Aginsky, V. N. Dating and Characterizing Writing, Stamp Pad, and Jet Printer Inks by Gas Chromatography/Mass Spectrometry. Int. J. Forensic Document Examiners. 1996, 2(2), 103–116.Google Scholar
  16. 16.
    Aginsky, V. N. Measuring Ink Extractibilty as a Function of Age—Why the Relative Aging Approach is Unreliable and Why it is More Correct to Measure Ink Volatile Components than Dyes. Int. J. Forensic Document Examiners 1998, 4(3), 214–230.Google Scholar
  17. 17.
    Fortini, A. Datation des encres: Tester la reproductibilite des measures de l’une des methods developpee par Aginsky (GC/MS), Universite de Lausanne, Institut de Police Scientifique, Seminaire de 4eme annee, 2000.Google Scholar
  18. 18.
    Weyermann, C.; Kirsch, D.; Costa-Vera, C.; Spengler, B. Dating of Ink Entries by MALDI/LDI-MS and GC-MS Analysis: Reality or Utopia? Proceedings of the 3rd European Academy of Forensic Science Meeting; Forensic Science International: Istanbul September 2003; pp 73–74.Google Scholar
  19. 19.
    Andrasko, J. Proceedings of the 3rd European Academy of Forensic Science Meeting. Forensic Science International: Istanbul September 2003; pp 73–74.Google Scholar
  20. 20.
    Lociciro, S.; Mazella, W.; Dujourdy, L.; Lock, E.; Margot, P. Dynamic of the Aging of Ballpoint Pen Inks. Science & Justice 2004, 44(3), 165–171.CrossRefGoogle Scholar
  21. 21.
    Aginsky, V. N. A Microspectrophotometric Method for Dating Ballpoint Inks—A Feasibility Study. J. Forensic Sci. 1995, 40, 475–478.CrossRefGoogle Scholar
  22. 22.
    Sakayanagi, M.; Komuro, J.; Konda, Y.; Watanabe, K.; Hirigaya, Y. Analysis of Ballpoint Pen Inks by Field Desorption Mass Spectrometry. J. Forensic Sci. 1999, 44(6), 1204–1214.CrossRefGoogle Scholar
  23. 23.
    Lyter, A. H. In Situ Molecular Analysis of Sequential Ink Writings by TOF-SIMS. Questioned Documents Section (Abtract). IAFS Meeting, Los Angeles, CA, August 1999.Google Scholar
  24. 24.
    Grim, D. M.; Siegel, J.; Allison, J. Evaluation of Desorption/Ionization Mass Spectrometric Methods in the Forensic Applications of the Analysis of Inks on Paper. J. Forensic Sci. 2001, 46(6), 1411–1420.CrossRefGoogle Scholar
  25. 25.
    Andrasko, J. HPLC Analysis of Ballpoint Pen Inks Stored at Different Light Conditions. J. Forensic Sci. 2001, 46(1), 21–30.CrossRefGoogle Scholar
  26. 26.
    Andrasko, J. Changes in Composition of Ballpoint Pen Inks on Aging in Darkness. J. Forensic Sci. 2001, 47(2), 324–327.Google Scholar
  27. 27.
    Grim, M. D.; Siegel, J.; Allison, J. Evaluation of Laser Desorption Mass Spectrometry and UV Accelerated Aging of Dyes on Paper as Tools for the Evaluation of a Questioned Document. J. Forensic Sci. 2002, 47(6), 1265–1273.Google Scholar
  28. 28.
    Weyermann, C.; Kirsch, D.; Andermann, T.; Spengler, B. Analysis of the Degradation Process of Ballpoint Ink by Mass Spectrometry. Poster Contribution at the 50th Annual Conference on Mass Spectrometry and Allied Topics; Orlando, FL, June, 2002; extended Abstract.Google Scholar
  29. 29.
    Li, X.; Liu, G.; Zhao, J. Two Competitive primary Processes in the Photodegradation of Cationic Triarylmethane Dyes Under Visibile Irradiation in TiO2 Dispersions. New J. Chem. 1999, 23, 1193–1196.CrossRefGoogle Scholar
  30. 30.
    Hess, J. The Black and White Report. Ink World; June 2000 pp 53–54.Google Scholar
  31. 31.
    Levinson, J. Questioned Documents: A Lawyer’s Handbook; Academic Press: London, 2001 pp 128–129.Google Scholar
  32. 32.
    Karas, M.; Bachmann, D.; Bahr, U.; Hillenkamp, F. Matrix-Assisted Ultraviolet Laser Desorption of Nonvolatile Compounds. Int. J. Mass Spectrom. Ion Processes 1987, 78, 53–68.CrossRefGoogle Scholar
  33. 33.
    Chaurand, P.; Luetzenkirchen, F.; Spengler, B. Peptide and Protein Identification by Matrix-Assisted Laser Desorption Ionization (MALDI) and MALDI-Post-Source Decay Time-of-Flight Mass Spectrometry. J. Am. Soc. Mass. Spectrom. 1999, 10, 91–103.CrossRefGoogle Scholar
  34. 34.
    Stewart, L. F. Artificial Aging of Documents. J. Forensic Sci. 1982, 27, 450–453.Google Scholar
  35. 35.
    Cantu, A. A. Comments on the Accelerated Aging of Documents. J. Forensic Sci. 1988, 33, 744–750.Google Scholar
  36. 36.
    Aginsky, V. N. Accelerated Aging—Its Use in Methods for Dating Ink, Letters. Int. J. Forensic Documents Examiners 1996, 2(3), 179–181.Google Scholar
  37. 37.
    Stewart, L. F.; Fortunato, S. L. Distinguishing Between Relative Ink Age Determinations and the Accelerated Aging Techniques. Int. J. Forensic Document Examiners 1996, 2(1), 10–15.Google Scholar
  38. 38.
    Weyermann, C.; Costa-Vera, C.; Kirsch, D.; Spengler, B. A Study of the Aging Processes of Ballpoint Dyes and Solvents by LDI-MS and GC/MS. Oral Presentation at the 17th International Symposium on the Forensic Sciences; Wellington, New Zealand, March, 2004; Abstract.Google Scholar

Copyright information

© American Society for Mass Spectrometry 2006

Authors and Affiliations

  • Céline Weyermann
    • 1
    • 2
  • Dieter Kirsch
    • 1
  • César Costa-Vera
    • 1
    • 3
  • Bernhard Spengler
    • 1
  1. 1.Institute of Inorganic and Analytical ChemistryJustus-Liebig University GiessenGiessenGermany
  2. 2.Institut de Police ScientifiqueLausanne University, BCH DorignyLausanneSwitzerland
  3. 3.Department of Physics, Escuela Politécnica NacionalLadron Guevara N.N. Ed. Ing. CivilQuitoEcuador

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