Analysis of Pigmented Inkjet Printer Inks and Printed Documents by Laser Desorption/Mass Spectrometry*,†

Abstract: Anyone with a computer, scanner, and color printer has the capability for creating documents such as identification cards, passports, and counterfeit currency. Laser desorption mass spectrometry (LDMS) has been demonstrated as a powerful tool for colorant analysis. Inkjet printers are now moving largely toward the use of pigments as colorants; their insolubility makes analysis by simpler methods such as thin‐layer chromatography no longer an option. Recent developments in pigmented inkjet printer inks, such as gloss optimizers that coat pigment particles, may prohibit colorant analysis by LDMS. We demonstrate here that pigments used in inks from two Epson printers can be detected and analyzed by LDMS. Also, LDMS spectra of various colors created using a 4‐cartridge (cyan/magenta/yellow/black, CMYK) inkset are evaluated, to begin to develop an approach for unraveling LDMS data from real samples, to determine the number of inks used by a printer, and the chemical composition of the colorants.     

Application of capillary electrophoresis to examination of color inkjet printing inks for forensic purposes

In the process of questioned document examination, the discrimination of inkjet printing inks is becoming more necessary due to increasingly frequent counterfeiting of documents printed by inkjet printers. Therefore, a method based on micellar electrophoretic capillary chromatography (MECC) has been developed and applied to analysis of such inks extracted from paper. With the use of an optimized and validated analytical procedure, multielectropherograms of inks taken from various models of printers made by various producers (Hewlett-Packard, Epson, Brother, Lexmark and Canon) were created. It was shown that effective differentiation of individual inks was possible in terms of migration time, order and specific shapes of characteristic peaks. By comparison of recorded UV-Vis spectra, the identification of main dyes was also achievable. The usefulness of the method was confirmed by an intralaboratory test of utility, in which several forged printouts were successfully examined. The obtained results proved that the proposed procedure is a useful tool that could be applied to ink discrimination and group identification of dyes originating from inkjet printing inks. Consequently, the developed method can be applied in the forensic field, including investigation of the authenticity of documents.     

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

Abstract:  Laser desorption mass spectrometry (LDMS) is emerging as a technique for questioned document examination. Its use is limited to detecting ink dyes that are neutral or singly charged. Several inks contain dyes that are multiply charged and LDMS cannot be employed for their identification. We have successfully detected >20 polyionic dyes that can be used in the manufacture of inks using matrix-assisted laser desorption/ionization (MALDI) MS, directly from paper, with the matrix, 2-(4-hydroxyphenylazo)benzoic acid (HABA), and the additive, diammonium hydrogen citrate (DAHC). For example, Acid Violet 49, a charged dye containing one positively-charged site and two negatively charged sulfonate groups, cannot be detected by LDMS, but forms intact, singly charged ions in the MALDI MS experiment. The method described is also useful for identifying multiply charged dye mixtures that are used in modern pen inks.     

Evaluation of desorption/ionization mass spectrometric methods in the forensic applications of the analysis of inks on paper.

Fast atom bombardment and laser desorption mass spectrometry (LDMS) provide molecular level information concerning an ink's composition. Two ink-jet printer inks, Ink A containing the cationic dye Methyl Violet 2B, and Ink B containing the anionic dye, Solvent Black, were studied. Both positive and negative ion detection modes of the mass spectrometer were used. LD may be used for the analysis of inks on paper. Once on paper, the ink's solvent system has evaporated, leaving mainly the dyes behind, which are detected using LDMS. An ink fades with time, indicating that the dyes are degrading. Preliminary results from an accelerated aging study of ballpoint pen ink using UV irradiation confirm that dye degradation products are formed. The degradation chemistry follows an oxidative demethylation process for which all products formed are detected using LDMS. Results suggest that LDMS may be developed to determine the relative age of inks.     

The Capability of Raman Microspectroscopy to Differentiate Printing Inks

This study applies Raman microspectroscopy to differentiate the chemical components in printing inks of different brands, colors, and type using the 532 nm and 785 nm excitation wavelengths. Spectra were collected from 319 inks (78 inkjet, 76 toner, 79 offset, and 86 intaglio) representing various colors. Comparisons were performed to calculate discrimination capability percentages for each ink type. Overall, Raman microspectroscopy differentiates according to the following hierarchy: intaglio (96%), inkjet (92%), offset (90%), and toner (61%). The ability of Raman microspectroscopy to differentiate between same‐colored inks from different brands was dependent on the color and ink analyzed. Based on ink color, the discrimination capability ranged from 75 to 94% (inkjet), 0 to 86% (toner), and 0 to 77% (offset). Copper phthalocyanine was detected in cyan inks and various intaglio inks, while carbon black was identified in black inkjet, offset, and intaglio inks.     

显微共焦拉曼光谱技术区分喷墨打印机打印的彩色图文墨迹

目的建立显微共焦拉曼光谱法区分喷墨打印机打印的彩色图文墨迹的方法。方法利用显微共焦拉曼光谱技术所具有微量、微区、原位分析及非破坏性等特点,对24种常见彩色墨水墨迹分别进行检验。结果品红色墨点墨迹成分归类区分效果最好,其次是黄色墨点,最后是蓝色墨点。结论采用显微共焦拉曼光谱技术对彩色打印墨迹进行不同颜色单点分析可大大提高喷墨打印机厂家型号的识别率,是一种有效的检测手段。     

Differentiating writing inks using direct analysis in real time mass spectrometry

Writing ink analysis is used in establishing document authenticity and the sources and relative ages of written entries. Most analytical methods require removing samples or visibly altering the document. Nondestructive, in situ analysis of writing inks on paper without visible alteration is possible using mass spectrometry with a new ion source called Direct Analysis in Real Time. Forty-three different black and blue ballpoint, black fluid, and black gel inks were examined. Both dyes and persistent but thermally labile components of the inks contribute to the mass spectra, principally as protonated molecules [M+H](+). Numerous ink components were identified from the spectra. The spectra were placed in a searchable library, which was then challenged with two spectra from each of the 43 inks. The best match for each of the challenge spectra was correct for all but one ink, which matched with a very similar ink by the same manufacturer.     

激光显微共聚焦拉曼光谱仪对红色墨迹的研究

目的利用激光显微共聚焦拉曼光谱仪对文书中常见的红色墨迹材料进行表征,研究该方法对红色墨迹材料的区分能力。方法在785nm激发波长,50倍物镜条件下,对49种红色印文,以及9种彩色喷墨打印和13种彩色激光打印的红色墨迹材料进行拉曼光谱表征。结果通过对71种墨迹样品的谱图进行分析,可以发现,红色印文墨迹、喷墨打印红色墨迹及激光打印红色墨迹的拉曼光谱间均存在差异,同时,拉曼光谱可将这三种墨迹材料分别进一步区分。结论显微共聚焦激光拉曼光谱可对红色墨迹材料进行有效表征和区分。这一方法可对红色印文墨迹进行识别,并且可实现对伪造印文文件的鉴别。     

Evaluation of laser desorption mass spectrometry and UV accelerated aging of dyes on paper as tools for the evaluation of a questioned document

Laser desorption mass spectrometry (LDMS) may be used for the detection and identification of dyes found in inks. Naturally-aged and artificially-aged blue and black ballpoint pen inks containing the cationic dye methyl violet were analyzed on paper. The average molecular weight of the dye sample was calculated from LD mass spectral data and plotted versus time. The resulting aging curves demonstrate that, as dye degradation increases, the average molecular weight of the dye decreases. Typical variables involved in ink aging, such as the type of paper and ink formulation, were investigated. Results show that these variables influence the rate of dye degradation. Furthermore, UV accelerated aging has been developed and tested as an alternative to thermal approaches.     

Ballpoint pen inks: characterization by positive and negative ion-electrospray ionization mass spectrometry for the forensic examination of writing inks

A method based on profiling of dye components by electrospray ionization mass spectrometry (ESI/MS) is described for the characterization of ballpoint pen inks. The method involves benzyl alcohol (30 microL) extraction of ink from paper. The extracts of ink lines 1 and 5 mm in length are used for direct ESI/MS analysis in positive and negative modes, respectively. The instrumental analysis takes 3 min. Basic and acid dyes in the inks are detected in the positive and negative modes, respectively, with each dye yielding one or two characteristic ion peaks. The mass spectrum, which is mainly a compositional signature of the dyes in the ink, was not affected by the type of paper from which the ink was extracted, or by natural ageing of the ink on document in the absence of light. However, exposure to fluorescent illumination caused dealkylation of polyalkylated basic dyes and resulted in changes in the homologous distribution of the dyes. In this study, a total of 44 blue inks, 23 black inks, and 10 red inks have been analyzed, and the mass spectra were used to establish a searchable library. ESI/MS analysis provides a simple and fast way to compare ink specimens and in combination with on-line library search permits rapid screening of inks for forensic document investigations.     

On the spectroscopic cum chemometric approach for differentiation and classification of inkjet,laser and photocopier printed documents

The potential of ATR-FTIR spectroscopy combined with chemometric methods is explored for the rapid and no-destructive forensic investigation of inkjet, laser and photocopier printed documents. The aim of the present study is to ascertain the source of origin of unknown printed documents, i.e., whether it belongs to the laser or inkjet or photocopier devices and also to visualize the intra-variations present in the same types of printed documents. It is observed that these printing inks contain polystyrene, bisphenol A, methyl acrylate and aromatic ethers as the main chemical constituents. The standard normal variate normalization is performed in order to eliminate the differences caused by the amount of toner powder/inks. The discrimination among printed documents is achieved by using chemometric methods including hierarchal cluster analysis and principal component analysis. Further, linear discriminant analysis is used to classify the unknown printed documents into its respective class of printing devices. The present methodology provides robust, non-destructive, reproducible, and simultaneous identification methods for printed documents.     

Photodegradation and laser desorption mass spectrometry for the characterization of dyes used in red pen inks

Photodegradation and laser desorption mass spectrometry (LDMS) is a powerful combination of methods capable of characterizing dyes found in pen inks. Rhodamine dyes in pens that contain red ink were analyzed directly from paper (no extraction step is necessary). Inks exposed to incandescent light form photodegradation products (compounds with lower molecular weights than that of the intact dye) and in some instances, photoproducts (compounds with higher molecular weights than that of the intact dye). The degradation products and photoproducts can be detected with LDMS, and the results can be used for dye identification. Advantages include: (1) the instrumental analysis takes less than a minute; (2) sample preparation is minimal; (3) LDMS is a minimally destructive technique; (4) incandescent light sources are inexpensive, safe to use, and readily available; and (5) isomeric dyes can be distinguished.     

Application of Raman Spectroscopy and Surface‐Enhanced Raman Scattering to the Analysis of Synthetic Dyes Found in Ballpoint Pen Inks*

Abstract: The applicability of Raman spectroscopy and surface‐enhanced Raman scattering (SERS) to the analysis of synthetic dyes commonly found in ballpoint inks was investigated in a comparative study. Spectra of 10 dyes were obtained using a dispersive system (633 nm, 785 nm lasers) and a Fourier transform system (1064 nm laser) under different analytical conditions (e.g., powdered pigments, solutions, thin layer chromatography [TLC] spots). While high fluorescence background and poor spectral quality often characterized the normal Raman spectra of the dyes studied, SERS was found to be generally helpful. Additionally, dye standards and a single ballpoint ink were developed on a TLC plate following a typical ink analysis procedure. SERS spectra were successfully collected directly from the TLC plate, thus demonstrating a possible forensic application for the technique.     

Application of Raman spectroscopy in forensic investigation of questioned documents involving stamp inks

Stamp pad inks from different manufacturers across India have been analyzed to investigate the feasibility of Raman scattering as a tool for forensic analysis of questioned documents involving stamp inks. Nine different stamping inks were analyzed by both Raman spectroscopic and HPTLC methods. The results demonstrate the effectiveness of these methods in classifying the investigated stamping inks based on their spectral pattern and HPTLC chromatogram. Raman scattering tool was able to determine the sequence of heterogeneous intersection strokes involving a blue stamp pad ink and other writing instruments, such as ballpoint pen ink (red and black), pencil and laser printer toner. However, this method was unable to resolve the exact sequencing for the intersection strokes involving investigated stamp ink and blue ballpoint ink or gel pen ink (all colors).     

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

The knowledge of the discriminating power of analytical techniques used for the differentiation of writing inks can be useful when interpreting results. Ultraviolet-visible (UV-VIS) spectrophotometry, thin layer chromatography (TLC), and diffuse reflectance Fourier transform infrared spectroscopy (FT-IR) were used to examine a population of 21 black and 12 blue ballpoint writing inks. Based on corroborative results of these methods, the discrimination power for UV-VIS, TLC, and FT-IR was determined to be 100% and 98% for the black and blue inks, respectively. Generally, TLC and UV-VIS can be used to differentiate the colorant components (i.e., dyes and some pigments) found in inks. As FT-IR can be utilized to identify some of the noncolorant components, it was determined to be an excellent complementary technique that can be implemented into an analytical scheme for ink analysis.     

Differentiation of ballpoint pen inks by thermodesorption and gas chromatography-mass spectrometry

Differentiation and classification of ink entries with dated samples of a reference collection are important aspects in the examination of questioned documents. Classification of writing inks is presently achieved by analysis of dyes and colorants contained in the ink. This technique has its limitations in newly developed ink formulations with identical dye composition but differing in their solvents and binder resins. This paper introduces a method for the determination of solvents and binder resins of an ink sample directly from paper without sample preparation. This aim is accomplished by thermodesorption of the sample followed by gas chromatography/mass spectroscopy. The method was tested on numerous samples of ballpoint pen inks, which were subsequently grouped into several solvent and resin subgroups. A case study shows the applicability of the newly developed method.     

书写材料的无损检验系统研究

本研究运用显微分光光度仪、文件检验仪和傅立叶变换拉曼光谱仪三种方法,分别对在中国市场上收集的不同厂家、牌号、型号的35种黑墨水、20种蓝黑墨水、22种蓝墨水、49种黑色墨水笔、30种蓝色墨水笔、45种黑色圆珠笔、和50种蓝色圆珠笔等七组样品进行非破坏检验。结果表明:(1三种非破坏检验方法都能单独对七组样品进行不同程度的鉴别,区分率在50%—94.4%之间;(2)三种方法联用后对黑墨水、蓝黑墨水、蓝墨水、黑色墨水笔、蓝色墨水笔、黑色圆珠笔和蓝色圆珠笔的区分率可分别提高到93.4%、97.3%、99.1%97.2%、97.2%、95.6%和91.8%。通过三种非破坏检验方法的联用,证明它们之间有较强的互补性,最大限度地提高了检验效应,可建立系统的非破坏检验方法。     

Source Determination of Red Gel Pen Inks using Raman Spectroscopy and Attenuated Total Reflectance Fourier Transform Infrared Spectroscopy combined with Pearson's Product Moment Correlation Coefficients and Principal Component Analysis

The potential combination of two nondestructive techniques, that is, Raman spectroscopy (RS) and attenuated total reflectance–fourier transform infrared (ATR‐FTIR) spectroscopy with Pearson's product moment correlation (PPMC) coefficient (r) and principal component analysis (PCA) to determine the actual source of red gel pen ink used to write a simulated threatening note, was examined. Eighteen (18) red gel pens purchased from Japan and Malaysia from November to December 2014 where one of the pens was used to write a simulated threatening note were analyzed using RS and ATR‐FTIR spectroscopy, respectively. The spectra of all the red gel pen inks including the ink deposited on the simulated threatening note gathered from the RS and ATR‐FTIR analyses were subjected to PPMC coefficient (r) calculation and principal component analysis (PCA). The coefficients r = 0.9985 and r = 0.9912 for pairwise combination of RS and ATR‐FTIR spectra respectively and similarities in terms of PC1 and PC2 scores of one of the inks to the ink deposited on the simulated threatening note substantiated the feasibility of combining RS and ATR‐FTIR spectroscopy with PPMC coefficient (r) and PCA for successful source determination of red gel pen inks. The development of pigment spectral library had allowed the ink deposited on the threatening note to be identified as XSL Poppy Red (CI Pigment Red 112).     

Application of Micro‐Attenuated Total Reflectance Fourier Transform Infrared Spectroscopy to Ink Examination in Signatures Written with Ballpoint Pen on Questioned Documents

Questioned documents examined in a forensic laboratory sometimes contain signatures written with ballpoint pen inks; these signatures were examined to assess the feasibility of micro‐attenuated total reflectance (ATR) Fourier transform infrared (FTIR) spectroscopy as a forensic tool. Micro‐ATR FTIR spectra for signatures written with 63 ballpoint pens available commercially in Korea were obtained and used to construct an FTIR spectral database. A library‐searching program was utilized to identify the manufacturer, blend, and model of each black ballpoint pen ink based upon their FTIR peak intensities, positions, and patterns in the spectral database. This FTIR technique was also successfully used in determining the sequence of homogeneous line intersections from the crossing lines of two ballpoint pen signatures. We have demonstrated with a set of sample documents that micro‐ATR FTIR is a viable nondestructive analytical method that can be used to identify the origin of the ballpoint pen ink used to mark signatures.     

Classification and individualization of black ballpoint pen inks using principal component analysis of UV-vis absorption spectra

The technique of principal component analysis has been applied to the UV-vis spectra of inks obtained from a wide range of black ballpoint pens available in the UK market. Both the pen ink and material extracted from the ink line on paper have been examined. Here, principal component analysis characterised each spectrum within a group through the numerical loadings attached to the first few principal components. Analysis of the spectra from multiple measurements on the same brand of pen showed excellent reproducibility and clear discrimination between inks that was supported by statistical analysis. Indeed it was possible to discriminate between the pen ink and the ink line from all brands examined in this way, suggesting that the solvent extraction process may have an influence on these results. For the complete set of 25 pens, interpretation of the loadings for the first few principal components showed that both the pen inks and the extracted ink lines may be classified in an objective manner and in agreement with the results of parallel thin layer chromatography studies. Within each class almost all inks could be individualised. Further work has shown that principal component analysis may be used to identify a particular ink from a database of reference UV-vis spectra and a strategy for developing this approach is suggested.