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Current Chromatography

Author(s): Carina M.B. de Carvalho*, Scorsatto R. Ortiz and Renata P. Limberger

DOI: 10.2174/2213240606666190410152956

Cite As
Manuscripts from Different Brands of Ballpoint Pens – GC/MS Ageing Profile in Brazilian Tropical Weather

Page: [15 - 29] Pages: 15

  • * (Excluding Mailing and Handling)

Abstract

Background: Dating of ballpoint pen manuscripts in forensic documents is still a challenge for experts. Methods of ink dating consider solvent evaporation through time, especially 2- phenoxyethanol (2-PE).

Objective: The objective of the researchers was to perform a continued study with pen ink strokes of ballpoint pens commercialized in Brazil, to characterize the ageing profile of 15 brands of blue and black pens.

Methods: Solvent composition analysis of ballpoint pen ink lines written in white and recycled paper was performed by gas chromatography/mass spectrometry, to quantify 2-PE, in recently written lines and in lines aged 4, 18, 27 and 36 months.

Results: The results showed that the pens had initial quantities of 2-PE smaller than in the Europe despite of having similar ageing behavior. Such kind of paper had more influence on aged pen strokes than in the recently applied pen strokes. Light and heat accelerated ageing. Some pens stopped ageing at 18, 27 and 36 months.

Conclusion: The results obtained were promising for elucidation of the ageing behavior of pen ink lines in tropical weather, but further statistical treatments could be done to adequate interpretation in real cases.

Keywords: Forensic chemistry, 2-phenoxyethanol, pen ink aging, document forgery, gas chromatography, mass spectrometry.

[1]
Andrasko, J. Changes in composition of ballpoint pen inks on aging in darkness. J. Forensic Sci., 2001, 47(2), 324-327.
[2]
Grim, D.M.; 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), 1-9.
[3]
Weyermann, C.; Kirsch, D.; Vera, C.C.; Spengler, B. Photofading of ballpoint dyes studied on paper by LDI and MALDI MS. J. Am. Soc. Mass Spect., 2006, 17, 297-306.
[4]
Weyermann, C.; Spengler, B. The potential of artificial aging for modeling of natural aging processes of ballpoint ink. Forensic Sci. Int., 2008, 180, 23-31.
[5]
Weyermann, C.; Kirsch, D.; Vera, C.C.; Spengler, B. Evaluation of the photodegradation of crystal violet upon light exposure by mass spectrometric and spectroscopic methods. Forensic Sci. Int., 2009, 54(2), 339-345.
[6]
Lalli, P.M.; Sanvido, G.B.; Garcia, J.S.; Cosso, R.G.; Maia, D.R.J.; Zacca, J.J.; Maldaner, A.O.; Eberlin, M.N. Fingerprinting and aging of ink by easy ambient sonic-spray ionization mass spectrometry. Analyst , 2010, 135, 745-750.
[7]
Aginsky, V.N. Measuring ink extractability 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 Doc. Exam., 1998, 4(3), 214-230.
[8]
Koenig, A.; Magnolon, S.; Weyermann, C. A comparative study of ballpoint ink aging parameters using GC/MS. Forensic Sci. Int., 2015, 252, 93-106.
[9]
Koenig, A.; Bügler, J.; Kirsch, D.; Köhler, F.; Weyermann, C. Ink dating using thermal desorption and gas chromatography/mass spectrometry: comparison of results obtained in two laboratories. J. Forensic Sci., 2015, 60(S1), 152-161.
[10]
San Román, I.; Bartolomé, L.; Alonso, M.L.; Alonso, R.M.; Ezcurra, M. DATINK pilot study: An effective methodology for ballpoint pen ink dating in questioned documents. Anal. Chim. Acta, 2015, 892, 105-114.
[11]
Diaz-Santana, O.; Vega-Moreno, D.; Conde-Hardisson, F. Gas chromatography-mass spectrometry and high-performance liquid chromatography-diode array detection for dating of paper ink. J. Chromatogr. A, 2017, 1515, 187-195.
[12]
Koenig, A.; Weyermann, C. Ink dating, part I: Statistical distribution of selected ageing parameters in a ballpoint inks reference population. Sci. Justice, 2018, 58(1), 17-30.
[13]
Stewart, L.F. Ballpoint ink age determination by volatile component comparison - a preliminary study. J. Forensic Sci., 1985, 30(2), 405-411.
[14]
Lociciro, S.; Dujourdy, L.; Mazzella, W.; Margot, P. Dynamic of the ageing of ballpoint pen inks: Quantification of phenoxyethanol by GC-MS. Sci. Justice, 2004, 44(3), 165-171.
[15]
Weyermann, C.; Kirsch, D.; Vera, C.C.; Spengler, B. A GC/MS study of the drying of ballpoint pen ink on paper. Forensic Sci. Int., 2007, 168, 119-127.
[16]
Brazeau, L.; Gaudreau, M. Ballpoint pen inks: The quantitative anaysis of ink solvents on paper by solid-phase microextraction. J. Forensic Sci., 2007, 52(1), 209-215.
[17]
Berger-Karin, C.; Hendriks, U.; Geyer-Lippmann, J. Comparison of natural and artificial aging of ballpoint inks. J. Forensic Sci., 2008, 53(4), 989-992.
[18]
Bügler, J.H.; Buchner, H.; Dallmayer, A. Age determination of ballpoint pen ink by thermal desorption and gas chromatography-mass spectrometry. J. Forensic Sci., 2008, 53(4), 982-988.
[19]
Diaz-Santana, O.; Conde-Hardisson, F.; Vega-Moreno, D. Comparison of the main dating methods for six ball-point pen inks. Microchem. J., 2018, 138, 550-551.
[20]
Weyermann, C.; Almog, J.; Bügler, J.; Cantu, A.A. Minimum requirements for application of ink dating methods based on solvent analysis casework. Forensic Sci. Int., 2011, 210, 52-62.
[21]
Carvalho, C.M.B. Analysis of the initial concentration of solvents from ballpoint pen ink. Revista Brasileira de Ciências Policiais, 2014, 5(1), 65-96.
[22]
Weyermann, C.; Schiffer, B.; Margot, P. A logical framework to ballpoint ink dating interpretation. Sci. Justice, 2008, 48, 118-125.
[23]
Wang, J.; Luo, G.; Sun, S.; Wang, Z.; Wang, Y. Systematic analysis of bulk blue ballpoint pen ink by FTIR spectrometry. J. Forensic Sci., 2001, 46(5), 1093-1097.
[24]
Silva, C.S.; Borba, F.S.L.; Pimentel, M.F.; Pontes, M.J.C.; Honorato, R.S.; Pasquini, C. Classification of blue pen ink using infrared spectroscopy and linear discriminant analysis. Microchem. J., 2013, 109, 122-127.
[25]
Sharma, V.; Kumar, R. Fourier transform infrared spectroscopy and high performance thin layer chromatography for characterization and multivariate discrimination 25of blue ballpoint pen ink for forensic applications. Vibrat. Spect., 2017, 92, 96-104.
[26]
Liu, Y.; Yu, J.; Xie, M.X.; Chen, Y.; Jiang, G.Y.; Gao, Y. Studies on the degradation of blue gel pen dyes by ion-pairing high performance liquid chromatography and electrospray tandem mass spectrometry. J. Chrom. A, 2006, 1125(1), 95-103.
[27]
Confortin, D.; Brustolon, M.; Franco, L.; Neevel, H.; Bommel, M.R. Crystal violet: Study of the photo-fading of an early synthetic dye in aqueous solution and on paper with HPLC-PDA, LCMS and FORS. J. Phys., 2010, 231012011
[28]
Freidenfelds, V.; Mekss, P. The possibilities of determination of the relative age of ballpoint pen ink entries by high performance liquid chromatography. Latv. J. Chem., 2012, 3, 242-248.
[29]
Williams, M.R.; Moody, C.; Arcenoux, L.; Rinke, C.; White, K.; Sigman, M.E. Analysis of black writing ink by electrospray ionization mass spectrometry. Forensic Sci. Int., 2009, 191, 97-103.
[30]
Carvalho, C.M.B.; Ortiz, R.S.; Limberger, R.P. Figures of merit evaluation of gc/ms method for quantification of 2-phenoxyethanol from ballpoint pen ink lines and determination of the influence of support paper on solvent extraction. Química . Nova, 2019, 42(1), 42-48.
[31]
Andrasko, J.; Kunicki, M. Inhomogeneity and aging of ballpoint pen inks inside of pen cartridges. J. Forensic Sci., 2005, 50(3), 1-6.
[32]
Grim, D.M.; Siegel, J.; Allison, J. Does ink age inside of a pen cartridge? J. Forensic Sci., 2002, 47(6), 1294-1297.
[33]
Cantu, A.A. A study of the evaporation of a solvent from a solution - application to writing ink aging. Forensic Sci. Int., 2012, 219, 119-128.