Trends of Forensic Analysis of Pen Ink Using Attenuated Total Reflectance Fourier Transform Infrared (ATR-FTIR) Spectroscopy

Putri Nabihah Abdul Khofar; Umi Kalsum Abdul Karim; Ezlan Elias; Muhd Fauzi Safian; Mohamed Izzharif Abdul Halim

doi:10.22146/ijc.72282

Trends of Forensic Analysis of Pen Ink Using Attenuated Total Reflectance Fourier Transform Infrared (ATR-FTIR) Spectroscopy

https://doi.org/10.22146/ijc.72282

Putri Nabihah Abdul Khofar⁽¹⁾, Umi Kalsum Abdul Karim⁽²⁾, Ezlan Elias⁽³⁾, Muhd Fauzi Safian⁽⁴⁾, Mohamed Izzharif Abdul Halim^(5*)

(1) Faculty of Applied Sciences, Universiti Teknologi MARA, 40450 Shah Alam, Selangor, Malaysia
(2) Faculty of Applied Sciences, Universiti Teknologi MARA Perak, 35400 Tapah, Perak, Malaysia
(3) Faculty of Applied Sciences, Universiti Teknologi MARA, 40450 Shah Alam, Selangor, Malaysia
(4) Faculty of Applied Sciences, Universiti Teknologi MARA, 40450 Shah Alam, Selangor, Malaysia
(5) Faculty of Applied Sciences, Universiti Teknologi MARA, 40450 Shah Alam, Selangor, Malaysia
(*) Corresponding Author

Abstract

Many articles have been published on ink analysis to assist Forensic Document Examiner (FDE) in examining questioned documents. Ink analysis encountered about 45% of ballpoint and 24% of gel pen in forensic cases. Typically, ink samples found on the documents are limited to small quantities, requiring non-destructive techniques to preserve the evidence. Previous studies on ink analysis cover about 80% of spectroscopy techniques, including the Attenuated Total Reflectance Fourier Transform Infrared (ATR-FTIR). FDE prefers ATR-FTIR to retain the legibility of evidence since ATR-FTIR is known as non-destructive, fast, reliable, and precise instrumentation. Various modifications and developments to this technique have been published. Therefore, this work reviews the trend of analysis performed on samples of the document and evaluates the current approaches to the capacity of using ATR-FTIR on such samples. Remarks on the comparison studies are also included.

Keywords

document examination; Fourier Transform Infrared Spectroscopy; ink analysis; pen ink; spectroscopy technique

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References

[1] Braz, A., López-López, M., and García-Ruiz, C., 2013, Raman spectroscopy for forensic analysis of inks in questioned documents, Forensic Sci. Int., 232 (1-3), 206–212.

[2] Calcerrada, M., and García-Ruiz, C., 2015, Analysis of questioned documents: A review, Anal. Chim. Acta, 853, 143–166.

[3] Alamilla, F., Calcerrada, M., García-Ruiz, C., and Torre, M., 2013, Forensic discrimination of blue ballpoint pens on documents by laser ablation inductively coupled plasma mass spectrometry and multivariate analysis, Forensic Sci. Int., 228 (1-3), 1–7.

[4] Lee, L.C., Liong, C.Y., and Jemain, A.A., 2018, Validity of the best practice in splitting data for hold-out validation strategy as performed on the ink strokes in the context of forensic science, Microchem. J., 139, 125–133.

[5] Hofmann, A., 2010, "Spectroscopic Techniques: I Spectrophotometric Techniques" in Principles and Techniques of Biochemistry and Molecular Biology, 7^th Ed., Eds. Wilson, K., and Walker, J., Cambridge University Press, Cambridge, UK, 477–521.

[6] Ziȩba-Palus, J., and Kunicki, M., 2006, Application of the micro-FTIR spectroscopy, Raman spectroscopy and XRF method examination of inks, Forensic Sci. Int., 158 (2-3), 164–172.

[7] Lee, J., Kim, S.H., Cho, Y.J., Nam, Y.S., Lee, K.B., and Lee, Y., 2014, Characterization and sequence determination of pen inks, red sealing inks, and laser toners by TOF-SIMS and ATR FTIR, Surf. Interface Anal., 46 (S1), 317–321.

[8] Causin, V., Casamassima, R., Marega, C., Maida, P., Schiavone, S., Marigo, A., and Villari, A., 2008, The discrimination potential of ultraviolet-visible spectrophotometry, thin layer chromatography, and Fourier transform infrared spectroscopy for the forensic analysis of black and blue ballpoint inks, J. Forensic Sci., 53 (6), 1468–1473.

[9] Halim, M.I.A., Aziz, N.S.A., Saim, N., Osman, R., and Jasmani, H., 2012, Statistical discrimination of blue ballpoint pen inks by infrared (IR) spectroscopy, Malays. J. Fundam. Appl. Sci., 8 (3), 155–161.

[10] Nam, Y.S., Park, J.S., Lee, Y., and Lee, K.B., 2014, Application of micro-attenuated total reflectance Fourier transform infrared spectroscopy to ink examination in signatures written with ballpoint pen on questioned documents, J. Forensic Sci., 59 (3), 800–805.

[11] Lee, L.C., Othman, M.R., and Pua, H., 2012, Systematic assessment of attenuated total reflectance-Fourier transforms infrared spectroscopy coupled with multivariate analysis for forensic analysis of black ballpoint pen inks, Malays. J. Anal. Sci., 16 (3), 262–272.

[12] Lee, L.C., Othman, M.R., Pua, H., and Ishak, A.A., 2012, Application of multivariate chemometry for discrimination of black ballpoint pen inks based on the IR spectrum, Malays. J. Forensic Sci., 3 (1), 5–10.

[13] Senior, S., Hamed, E., Masoud, M., and Shehata, E., 2012, Characterization and dating of blue ballpoint pen inks using principal component analysis of UV-Vis absorption spectra, IR spectroscopy, and HPTLC, J. Forensic Sci., 57 (4), 1087–1093.

[14] Feraru, D.L., Meghea, A., and Badea, N., 2013, Forensic discrimination of ballpoint pen inks based on correlation of data obtained by optical and spectral methods, Rev. Chim., 64 (1), 74–80.

[15] Halim, M.I.A., Saim, N., Osman, R., Jasmani, H., and Aziz, N.S.A., 2013, Multivariate chemometric discrimination of blue gel-pen inks by Fourier transform infrared spectroscopy, 2013 IEEE Symposium on Computers & Informatics (ISCI), Langkawi, Malaysia, 236–240.

[16] Silva, C.S., Borba, F.D.S.L., Pimentel, M.F., Pontes, M.J.C., Honorato, R.S., and Pasquini, C., 2013, Classification of blue pen ink using infrared spectroscopy and linear discriminant analysis, Microchem. J., 109, 122–127.

[17] Lee, L.C., 2014, Investigating Between-model variation of the PaperMate® pen using infrared spectrum and multivariate statistical techniques, Forensic Sci. J., 13 (1), 15–22.

[18] Sharma, N., and Agarwal, A., 2014, Analysis of blue fountain pen inks, Pharma Chem., 6 (1), 448–452.

[19] Durney, L., 2015, Using Vibrational Spectroscopy to Analyse the Effect of Environmental Aging on Gel Pen Inks, Thesis, University of Central Lancashire.

[20] Gazy, M., Eldebss, T., El-Zawawy, W., Helal, M., and Rashed, K., 2015, Comparative study between blue ballpoint pen inks and blue erasable pen inks by using spectroscopic analysis and chromatography method, Nat. Sci., 13 (12), 16–27.

[21] Garrappa, S., Germinario, G., Van Der Werf, I.D., Mirabile, A., and Sabbatini, L., 2016, Multi-analytical study of artist felt-tip pen inks, IMEKO International Conference on Metrology for Archaeology and Cultural Heritage, October 19–21, 2016, Torino, Italy, 136–139.

[22] Kamil, M., Mohamad Asri, M.N., Mat Desa, W.N.S., and Ismail, D., 2015, Fourier transform infrared (FTIR) spectroscopy and principal component analysis (PCA) of unbranded black ballpoint pen inks, Malays. J. Forensic Sci., 6 (1), 48–53.

[23] Sharma, V., Kumar, R., Devgan, K., Mishra, P. K., Ekielski, A., Kumar, V., and Kumar, V., 2018, Multivariate analysis for forensic characterization, discrimination, and classification of marker pen inks, Spectrosc. Lett., 51 (5), 205–215.

[24] Nunkoo, M.I., Saib-Sunassy, M.B., Li Kam Wah, H., and Jhaumeer Laulloo, S., 2016, "Forensic Analysis of Black, Blue, Red, and Green Ballpoint Pen Inks" in Crystallizing Ideas – The Role of Chemistry, Eds. Ramasami, P., Gupta Bhowon, M., Jhaumeer Laulloo, S., and Li Kam Wah, H., Springer International Publishing, Cham, Switzerland, 323–339.

[25] Yadav, J., and Yadav, L., 2018, Characterization of ballpoint pen ink by using non-destructive methods, Res. J. Forensic Sci., 6 (6), 1–6.

[26] e Brito, L.R., Martins, A.R., Braz, A., Chaves, A.B., Braga, J.W., and Pimentel, M.F., 2017, Critical review and trends in forensic investigations of crossing ink lines, TrAC, Trends Anal. Chem., 94, 54–69.

[27] Sharma, V., and Kumar, R., 2017, Fourier transform infrared spectroscopy and high performance thin layer chromatography for characterization and multivariate discrimination of blue ballpoint pen ink for forensic applications, Vib. Spectrosc., 92, 96–104.

[28] Zaffino, C., Passaretti, A., Poldi, G., Fratelli, M., Tibiletti, A., Bestetti, R., Saccani, I., Guglielmi, V., and Bruni, S., 2017, A multi-technique approach to the chemical characterization of colored inks in contemporary art: The materials of Lucio Fontana, J. Cult. Heritage, 23, 87–97.

[29] Lee, L.C., Liong, C.Y., and Jemain, A.A., 2018, Effects of data pre-processing methods on classification of ATR-FTIR spectra of pen inks using partial least squares-discriminant analysis (PLS-DA), Chemom. Intell. Lab. Syst., 182, 90–100.

[30] Said, H.M., and Ismail, D., 2018, Study on the effect of ageing to gel pen ink on papers using attenuated reflectant mode Fourier transform infrared (ATR-FTIR) spectroscopy, TIJMS, 3 (1), 38–43.

[31] Bansinge, M.D., Tekade, P.V., Bajaj, S.D., Mahodaya, O.A., and Barwat, N.A., 2019, Analysis of different ball point pen inks using thin layer chromatography and comparison with FTIR spectrometer, Chem. Sci. Trans., 8 (2), 160–171.

[32] Lee, L.C., and Jemain, A.A., 2019, Predictive modelling of colossal ATR-FTIR spectral data using PLS-DA: Empirical differences between PLS1-DA and PLS2-DA algorithms, Analyst, 144 (8), 2670–2678.

[33] Sharif, M., Batool, M., Chand, S., Farooqi, Z.H., Tirmazi, S.A.A.S., and Athar, M., 2019, Forensic discrimination potential of blue, black, green, and red colored fountain pen inks commercially used in pakistan, by UV/visible spectroscopy, thin layer chromatography, and fourier transform infrared spectroscopy, Int. J. Anal. Chem., 2019, 5980967.

[34] Kivioja, A., Hartus, T., Vuorinen, T., Gane, P., and Jaaskelainen, A.S., 2013, 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., 67 (6), 661–671.

[35] Wang, J., Luo, G., Sun, S., Wang, Z., and Wang, Y., 2001, Systematic analysis of bulk blue ballpoint pen ink by FTIR spectrometry, J. Forensic Sci., 46 (5), 1093–1097.

[36] Causin, V., Marega, C., Marigo, A., Casamassima, R., Peluso, G., and Ripani, L., 2010, Forensic differentiation of paper by X-ray diffraction and infrared spectroscopy, Forensic Sci. Int., 197 (1-3), 70–74.

[37] Gautam, R., Chauhan, R., Kumar, R., and Sharma, V., 2021, PLS-DA and infrared spectroscopy based rapid and non-destructive discrimination of black ball and gel pen inks for forensic application, Forensic Sci. Int.: Rep., 3, 100162.

[38] Lee, L.C., Liong, C.Y., and Jemain, A.A., 2016, Applying fourier-transform infrared spectroscopy and self- organizing maps for forensic classification of white-copy papers, Int. J. Adv. Sci. Eng. Inf. Technol., 6 (6), 1033–1039.

[39] Kumar, R., and Sharma, V., 2018, Chemometrics in forensic science, TrAC, Trends Anal. Chem., 105, 191–201.

[40] Sauzier, G., McGinn, J., Trubshoe, T., and Lewis, S.W., 2019, In situ examination of handwritten blue ballpoint inks using video spectral comparison with chemometrics, Forensic Sci. Int.: Rep., 1, 100021.

[41] Gannetion, L., Noor, S.N.M.M., Lim, P.Y., Chang, K.H., and Abdullah, A.F.L., 2021, Forensic discrimination of blue pen inks: Emergence of hybrid pen inks, Malays. J. Anal. Sci., 25 (4), 584–595.

[42] Halim, M.I.A., Saim, N., Osman, R., Jasmani, H., and Aziz, N.S.A., 2012, Multivariate Chemometric Discrimination of Black Ballpoint Pen Inks Based on Infrared Spectra, 2012 IEEE Symposium, Business, Engineering and Industrial Application, Bandung, Indonesia, 834–837.

DOI: https://doi.org/10.22146/ijc.72282