Analysis of Ballpoint Pen Inks by Field Desorption Mass Spectrometry

Sakayanagi, Masataka; Komuro, Jun; Konda, Yaeko; Watanabe, Kunio; Harigaya, Yoshihiro

doi:10.1520/jfs14588j

Cited by 26 publications

(23 citation statements)

References 8 publications

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“…After deposition on paper, the ink composition begins to change qualitatively and quantitatively: the resins polymerize, the solvents evaporate, and the dyes fade. Throughout the years, many different methods were developed to measure the changes occurring in the ink with time [1][2][3][4][5][6][7]: decrease of extractability of ink through hardening of the resins [8 -13, 16], disappearance of solvents [14 -20], and degradation of dyes [18,[21][22][23][24][25][26][27][28][29]. The analysis of the latter compounds involve techniques such as microspectrophotometry [21], HPLC analysis [25,26], or recently mass spectrometry [18, 22-24, 27, 28].…”

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confidence: 99%

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

Weyermann

Kirsch

Vera

et al. 2006

J. Am. Soc. Mass Spectrom.

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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. n the field of forensic examination of questioned documents, the legitimacy of an ink entry is often an essential question, and the possibility of determining the age of an ink stroke would definitely help to resolve this problem. Ballpoint pens are very common scriptural instruments, the inks of which contain equivalent amounts of dyes, solvents, and resins. After deposition on paper, the ink composition begins to change qualitatively and quantitatively: the resins polymerize, the solvents evaporate, and the dyes fade. Throughout the years, many different methods were developed to measure the changes occurring in the ink with time [1][2][3][4][5][6][7]: decrease of extractability of ink through hardening of the resins [8 -13, 16], disappearance of solvents [14 -20], and degradation of dyes [18,[21][22][23][24][25][26][27][28][29]. The analysis of the latter compounds involve techniques such as microspectrophotometry [21], HPLC analysis [25,26], or recently mass spectrometry [18, 22-24, 27, 28]. Laser desorption/ionization mass spectrometry (LDI-MS) i...

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confidence: 99%

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

Weyermann

Kirsch

Vera

et al. 2006

J. Am. Soc. Mass Spectrom.

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“…Dyes and solvents were identified by comparison of their UV-VIS and MS spectra with literature and reference data [1,5,6].…”

Section: Determination Of the Chemical Composition Of Ink And Data Prmentioning

confidence: 99%

The Possibilities of Determination of the Relative Age of Ballpoint Pen Ink Entries by High Performance Liquid Chromatography / Lodīšu Pildspalvas Tintes Ierakstu Relatīvā Vecuma Noteikšanas Iespējas Ar Augstefektīvās Šķidrumu Hromatogrāfijas Metodi

Freidenfelds¹,

Mekss²

2012

Latvian Journal of Chemistry

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Investigation of three colour inks was performed using the HPLC method. The research is based on the theory of reducing of solvent in ink and on the change of ratio between dyes due to the degradation of the dye or changes of its extraction properties. Old samples, aged from 1 to 7 months were selected for research. Samples were made using blue, violet and black ballpoint ink. Record samples are kept in the dark, in climatic conditions of a usual office. During the identification of ink compound, by using LC/MS, a statement was made that each ink sample contains 2-phenoxyethanol as a solvent, Methyl Violet and Basic Blue dyes and their degradation products. The areas of peaks gained at characteristic wavelengths are used for the analysis of the aging process.

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“…Visual examination scrutinizes colour and the morphology of the line [12,13]. Optical techniques utilising examination with visible, ultraviolet (UV) and infrared (IR) light are common [1,14]. IR examination has been extensively researched, particularly Fourier transform, Raman and microscopical reflection-absorption IR methods [6,[15][16][17][18][19].…”

Section: Document Analysismentioning

confidence: 99%

“…Other techniques include capillary electrophoresis (CE) [10,32], inductively coupled plasma mass spectrometry (ICP-MS) [33,34], laser ablation ICP-MS [35], field desorption mass spectrometry (FD-MS) [14] and ion-electrospray ionization mass spectrometry (ESI-MS) [4]. FD-MS, ESI-MS, ICP-MS, and to a slightly lesser extent LA-ICP-MS, remain semi-destructive techniques as they require the dissolution or removal of the ink from the paper in order to perform the analysis.…”

Section: Document Analysismentioning

confidence: 99%