Effectiveness of UV-Visible Spectroscopy (with Multi-Mode Plate Reader) and ATR-FTIR for the Discrimination of Black Marker Inks : A Chemometric Approach
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Abstract
In the ambit of Forensic examination of the questioned documents, writing instruments often serve as an essential tool in disclosing the legitimacy of a document. In the present study, a total of 18 marker samples including 9 permanent and 9 whiteboard (commonly known as dry erase) markers of black color of different brands were purchased from the local market of district Jhansi, Uttar Pradesh, India. UV-Visible spectroscopy with Multi-Mode Plate Reader and ATR-FTIR spectroscopy were used for the discrimination of samples. In the case of permanent marker inks, peaks near 390-405 nm and at 570-585 nm were found to be more prominent and differentiating than that of the whiteboard marker inks. Qualitative comparative analysis of the permanent and the whiteboard black marker ink samples showed 97.2% and 91.6% DP respectively based on their UV-Vis. spectral responses. FTIR spectroscopy of whiteboard markers confirmed the presence of characteristic peak at 1743 cm-1 (C=O stretch) together with a doublet in the region 2920-2850 cm-1 corresponding to asymmetric and symmetric C-H stretch in almost all the whiteboard marker inks, whereas in case of permanent marker inks the former peak 1743 cm-1 was completely absent and the later appeared as a single peak around 2900 cm-1. The results obtained from ATR-FTIR was analyzed using multivariate techniques such as PCA and DFA. PCA was used for the segregation of samples into different groups, whereas DFA was used for the discrimination and classification of marker ink samples. DFA provided a correct classification of 88.9% of the marker ink samples analyzed by FTIR. It is concluded that Multi Mode Plate Reader can be used as a substantial tool for the discrimination of marker inks and was found to be fast and cost effective with high throughput. Moreover, ATR-FTIR results gave some additional information related to the chemical composition of the samples and provided better discrimination when coupled with chemometrics.
Keywords
Forensic science, PCA, DFA, Marker ink discrimination, Document examination, Black marker inks, Photometric analysis
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References
Ellen D, Day S, Davies C. Scientific Examination of Documents: Methods and Techniques (4th ed.). CRC Press; 2021.
Mohamed Sadiq NS, Abdullah II, Mohamad Noor SNM, Wong KY, Chang KH, Abdullah AFL. Evaluation of the Performance of Erasable Marker Pen Ink for the Development of Indentations on Documents upon Surface Charging by Electrostatic Detection Device. J. Can. Soc. Forensic Sci. 2022;55(2):57-70. DOI: 10.1080/00085030.2021.2016160
Katz E, Halámek, J. Forensic Science: A Multidisciplinary Approach, John Wiley & Sons; 2016.
Mayer R. The Artist’s Handbook of Materials & Techniques (5th ed.), Revised and Updated. Viking; 1991.
Ragheb SAA, Salhab AS, Amr SS. Suicide by Xylene Ingestion: A Case Report and Review of Literature. Am J Forensic Med and Patho. 1986;7(4):327-29. https://doi.org/10.1097/00000433-198612000-00012
Wani SA, Al Salmi LA, Habib O, Ul Haq MU. Use of Permanent Markers for Intraoperative Marking in Body Contouring Surgery: An Innovative Technique. World J. Plast. Surg. 2018;7(3):387-88. https://doi.org/10.29252/wjps.7.3.387.
Causin V, Casamassima R, Marega C, Maida P, Schiavone S, Marigo A, Villari A. 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. 2008;53(6):1468-76. https://doi.org/10.1111/j.1556-4029.2008.00867.x.
Sharif M, Batool M, Chand S, Farooqi ZH, Tirmazi SAAS, Athar M. 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: 1-10. https://doi.org/10.1155/2019/5980967
Bansinge MD, Tekade PV, Bajaj SD, Mahodaya OA, Barwat NA. Analysis of Different Ball Point Pen Inks using Thin Layer Chromatography and Comparison with FTIR Spectrometer. Chem. Sci. Trans. 2019;8(2):160–171.
Król M, Kula A, Wietecha-Posłuszny R, Woźniakiewicz M, Kościelniak P. Examination of Black Inkjet Printing Inks by Capillary Electrophoresis. Talanta, 2012;96: 236-42. https://doi.org/10.1016/j.talanta.2011.12.025
Weyermann C, Kirsch D, Vera CC, Spengler B. A GC/MS Study of the Drying of Ballpoint Pen Ink on Paper. Forensic Sci Int. 2007;168(2-3):119-27. https://doi.org/10.1016/j.forsciint.2006.06.076
Saini K, Rathore R. Differentiation of Gel Pen Inks by Using High Performance Thin Layer Chromatography and Gas Chromatography-Mass Spectrometry. Malaysian Journal of Forensic Sciences, 2018;8(2):10-17.
Kher A, Mulholland M, Green E, Reedy B. Forensic Classification of Ballpoint Pen Inks Using High Performance Liquid Chromatography and Infrared Spectroscopy with Principal Components Analysis and Linear Discriminant Analysis. Vib. Spectrosc. 2006;40(2):270-77. https://doi.org/10.1016/j.vibspec.2005.11.002
Gawad AA, Salama TM, Meshref M, Mohmed GG, Zedan AF. Coupling ATR-FTIR Spectroscopy and Chemometric Analysis for Rapid and Non-destructive Ink Discrimination of Forensic Documents. Egypt. J. Chem. 2022;65(8):471-481.
Abdul Khofar PN, Abdul Karim UK, Elias E, Safian MF, Abdul Halim MI. Trends of Forensic Analysis of Pen Ink Using Attenuated Total Reflectance Fourier Transform Infrared (ATR-FTIR) Spectroscopy. Indones. J. Chem. 2022;22(4):1144-1154.
Ziȩba-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):164-172.
Imperio E, Giancane G, Valli L. Spectral Characterization of Postage Stamp Printing Inks by Means of Raman Spectroscopy. Analyst. 2015;140(5):1702-1710.
Kirby DP, Khandekar N, Sutherland K, Price BA. (2009). Applications of Laser Desorption Mass Spectrometry for the Study of Synthetic Organic Pigments in Works of Art. Int. J. Mass Spectrom. 2009;284(1-3):115-22. https://doi.org/10.1016./J.ijms.2008.08.011
Soltzberg LJ, Hagar A, Kridaratikorn S, Mattson A, Newman R. MALDI-TOF Mass Spectrometric Identification of Dyes and Pigments. J Am Soc Mass Spectrom. 2007;18(11):2001-06. https://doi.org/10.1016/j.jasms.2007.08.008
Alamilla F, Calcerrada M, García-Ruiz C, Torre M. Forensic Discrimination of Blue Ballpoint Pens on Documents by Laser Ablation Inductively Coupled Plasma Mass Spectrometry and Multivariate Analysis. Forensic Sci. Int. 2013;228(1-3):1–7.
Kula A, Wietecha-Posluszny R, Pasionek K, Krol M, Wozniakiewicz M, Koscielniak P. Application of laser induced breakdown spectroscopy to examination of writing inks for forensic purposes. Science and Justice. 2014;118-125.
Lennard C, El-Deftar MM, Robertson J. Forensic application of laser induced breakdown spectroscopy for the discrimination of questioned documents. Forensic Sci Int. 2015;254: 68-79.
Trejos T, Flores A, Almirall JR. Micro-spectrochemical analysis of document paper and gel inks by laser ablation inductively coupled plasma mass spectrometry and laser induced breakdown spectroscopy. Spectrochimica Acta Part B. 2010; 884-895.
Germinario G, Garrappa S, D’ Ambrosia V, van der Werf ID, Sabbatini L. Chemical composition of felt tip pen inks. Anal Bioanal Chem. 2018; 410(3): 1079-94.
Dunn JD, Allison J. The detection of multiply charged dyes using matrix-assisted laser desorption/ionization mass spectrometry for the forensic examination of pen ink dyes directly from paper, J. Forensic Sci. 2007; 52: 1205–1211, https://doi. org/10.1111/j.1556-4029.2007.00535.x.
Wu, V, Zhou C, Yu J, Liu H, Xie M, Differentiation and dating of gel pen ink entries on paper by laser desorption ionization- and quadruple-time of flight mass spectrometry, Dyes Pigm. 2012; 94: 525–532, https://doi.org/10.1016/j. dyepig.2012.03.005.
Weyermann C, Kirsch D, Costa-Vera C, Spengler B, Photofading of ballpoint dyes studied on paper by LDI and MALDI MS, J. Am. Soc. Mass Spectrom. 2006; 17: 297–306, https://doi.org/10.1016/j.jasms.2005.11.010.
Bojko K, Roux C, Reddy BJ. An examination of the sequence of intersecting lines using attenuated total reflectance-fourier transform infrared spectral imaging, J. Forensic Sci. 2008; 53: 1458–1467, https://doi.org/10.1111/j.1556- 4029.2008.00796.x.
Braz A, Lopez-Lopez M, Gracia-Ruiz C. Raman spectroscopy for forensic analysis of inks in questioned documents, Forensic Sci. Int. 2013; 232: 206–212, https://doi.org/10.1016/j.forsciint.2013.07.017.
Lutzenkirchen-Hecht D, Rohrmann K, Stoecker T, Thiel W., XPS investigations of ink-jet printed paper, Surf. Interface Anal. 2007; 39: 845–851, https://doi.org/ 10.1002/sia.2595.
Almirall, JR, Trejos T., Applications of LA-ICP-MS to Forensic Science, Elements. 12 (2016) 335–340. 10.2113/gselements.12.5.335.
Denman JA, Skinner WM, Kirkbride KP, Kempson IM. Organic and inorganic discrimination of ballpoint pen inks by ToF-SIMS and multivariate statistics, Appl. Surface Sci. 2010; 256(7): 2155–2163, https://doi.org/10.1016/j.apsusc.2009.09.066.
Lofgren A., Andrasko J., HPLC analysis of printing inks. J. For. Sci. 1993; 38: (5) 1151- 1160.
Wang XF, Yu J, Xie MX, Yao YT, Han J, Identification and dating of the fountain pen ink entries on documents by ion pairing high performance liquid chromatography, Forensic Sci. Int. 2008; 180: 43-49.
Kher A A, Green E V, Mulholland M I. Evaluation of principal components analysis with high performance liquid chromatography and photodiode array detection for the forensic differentiation of ball point pen inks, ASTM Int. 2001; 46 (4) 878.
Varshney K M, Jettappa T, Mehrotra V K, Baggi T R, Ink analysis from typed script of electronic typewriters by high performance thin layer chromatography, For. Sci. Inter. 1995; 72: 107-115.
Smalldon KW, Moffat AC. The Calculation of Discriminating Power for a Series of Correlated Attributes. J Forensic Sci Soc. 1973;13(4):291-95. https://doi.org/10.1016/s0015-7368(73)70828-8
Daszykowski M, Kaczmarek K, Vander Heyden Y, Walczak B. Robust Statistics in Data Analysis — A Review Basic Concepts. Chemom. Intell. Lab. Syst. 2007; 85: 203–219.
McLachlan G. Discriminant Analysis and Statistical Pattern Recognition, John Wiley and Sons; 2004.
Verma N, Kumar R, Sharma V. Analysis of Laser Printer and Photocopier Toners by Spectral Properties and Chemometrics. Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy. 2018; 196: 40-48. https://doi.org/10.1016/j.saa.2018.02.001
Abdi H, Williams LJ. Principal Component Analysis, Wiley Interdiscip. 2010: 433–459.
Bro R, Smilde AK, Principal Component Analysis. Anal. Methods. 2014; 6: 2812–2831.
Gromski, PS, Correa E, Vaughan AA, Wedge DC, Turner ML, Goodacre R. A Comparison of Different Chemometrics Approaches for the Robust Classification of Electronic Nose Data. Anal. Bioanal. Chem. 2014; 406: 7581–7590.
Lee LC, Liong CY, Osman K, Jemain AA. Comparison of Several Variants of Principal Component Analysis (PCA) on Forensic Analysis of Paper Based on IR spectrum. AIP Conference Proceedings. 2016;1750(1):060012. https://doi.org/10.1063/1.4954617
Van Der Werf ID, Germinario G, Palmisano F, Sabbatini L. Characterisation of Permanent Markers by Pyrolysis Gas Chromatography–Mass Spectrometry. Anal Bioanal Chem. 2011;399: 3483-490. https://doi.org/10.1007/s00216-011-4714-z
Sharma V, Kumar R, Devgan K, Mishra PK, Ekielski A, Kumar V, Kumar V. Multivariate Analysis for Forensic Characterization, Discrimination, and Classification of Marker Pen Inks. Spectrosc Lett. 2018;51(5):205-215. https://doi.org/10.1080/00387010.2018.1452265
Brinskelle P, Koenig E, Sendlhofer G, Baumhackl KA, Winter R, Sawetz I, Kamolz LP, Steinmetz I, Friedl H, Lumenta DB. Is there a Risk for Bacterial Transmission from Surgical Marker Pens?. J Hospital Infection. 2020;106(2):254-57. https://doi.org/10.1016/j.jhin.2020.08.003
Awab H, Mohd Jar AD, Yong WK, Ahmad UK. Infrared Spectroscopic Technique for the Forensic Discrimination of Marker Pen Inks. Malaysian J Forensic Sci. 2011;2(1):1-7.
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