Raman spectroscopy and laser desorption mass spectrometry for minimal destructive forensic analysis of black and color inkjet printed documents

Inkjet ink analysis is the best way to discriminate between printed documents, or even though more difficult, to connect an inkjet printed document with a brand or model of printers. Raman spectroscopy and laser desorption mass spectrometry (LDMS) have been demonstrated as powerful tools for dyes and pigments analysis, which are ink components. The aim of this work is to evaluate the aforementioned techniques for inkjet inks analysis in terms of discriminating power, information quality, and nondestructive capability. So, we investigated 10 different inkjet ink cartridges (primary colors and black), 7 from the HP manufacturer and one each from Epson, Canon and Lexmark. This paper demonstrates the capabilities of three methods: Raman spectroscopy, LDMS and MALDI-MS. Raman spectroscopy, as it is preferable to try the nondestructive approach first, is successfully adapted to the analysis of color printed documents in most cases. For analysis of color inkjet inks by LDMS, we show that a MALDI matrix (9-aminoacridine, 9AA) is needed to desorb and to ionize dyes from most inkjet inks (except Epson inks). Therefore, a method was developed to apply the 9AA MALDI matrix directly onto the piece of paper while avoiding analyte spreading. The obtained mass spectra are very discriminating and lead to information about ink additives and paper compositions. Discrimination of black inkjet printed documents is more difficult because of the common use of carbon black as the principal pigment. We show for the first time the possibility to discriminate between two black-printed documents coming from different, as well as from the same, manufacturers. Mass spectra recorded from black inks in positive ion mode LDMS detect polyethylene glycol polymers which have characteristic mass distributions and end groups. Moreover, software has been developed for rapid and objective comparison of the low mass range of these positive mode LDMS spectra which have characteristic unknown peaks.     

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。     

The Classification of Inkjet Inks Using AccuTOF™ DART™ (Direct Analysis in Real Time) Mass Spectrometry—A Preliminary Study

A novel approach for the analysis of inkjet inks is being reported. A time‐of‐flight mass spectrometer, coupled with a Direct Analysis in Real Time (DART?) ion source (AccuTOF? DART?), was used to determine if inkjet inks from various manufacturers and models of printers could be reliably differentiated, characterized, and identified. A total of 217 ink standards were analyzed. As inkjet printing often involves the use of multiple colors (e.g., cyan, magenta, yellow, and black) to form an image or text, two different approaches to creating a library of standards and sampling methods were evaluated for implementation in a standard operating procedure. This research will show that a microscopic examination of the region of interest is requisite to identify what colors were utilized during the printing process, prior to comparing with known standards. Finally, blind testing was administered with 10 unknown samples to assess the validity and accuracy of the methodology.     

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.     

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.     

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.     

The use of an electrostatic detection device to identify individual and class characteristics on documents produced by printers and copiers--a preliminary study

The market is inundated with inkjet printers, laser printers, and photocopiers, which are often used in criminal activities. Many of these office machines are built by various manufacturers, hence they are constructed with different hardware designs (e.g. "rolling" and "grabbing" mechanisms) that have changed over the years due to technological advances. Examinations of printed documents that involve the chemical analysis of ink colorants and the identification of physical machine defects such as trash marks are essential for the forensic examiner, but new techniques are needed to more closely identify a machine model or group of models. An electrostatic detection device (EDD) provide forensic examiners with a nondestructive method to examine indentations on a document. In this work, an EDD is used to detect latent physical markings left on documents by printers and photocopiers. Seventeen inkjet printers, 12 laser printers, and 3 photocopy machines were used to produce test documents. Physical markings were detectable in the large majority of the documents and were reproducible 100% of the time.     

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。     

Preliminary Study on Determining the Sequence of Intersecting Lines by Fluorescence Technique

The determination of the sequence of intersecting lines is an important part of questioned document examinations. A fluorescence technique was used to determine the sequence of heterogeneous intersecting lines produced using inkpad ink, stamp‐pad ink, ballpoint pens, gel pens, fountain pens, colorants of carbon paper, photocopiers, laser printers, and inkjet printers. A SteREO Discovery.V20 equipped with the ZEN Blue Lite software was chosen to perform the tests.As the results obtained from the study were positive under most conditions, the fluorescence technique was found to be very successful in determining the sequence of intersecting lines from ballpoint pen, gel pen, fountain pen, photocopier, laser and inkjet printers, and inkpad inks. The method was also successful in determining the sequence of intersecting lines from ballpoint pen, photocopier, laser printer, and stamp‐pad inks under most conditions. The technique was not successful in determining the order of crossing lines blending together.     

Evaluation of the Forensic Utility of Scanning Electron Microscopy‐Energy Dispersive Spectroscopy and Laser Ablation‐Inductively Coupled Plasma‐Mass Spectrometry for Printing Ink Examinations

Improvements in printing technology have exacerbated the problem of document counterfeiting, prompting the need for analytical techniques that better characterize inks for forensic analysis and comparisons. In this study, 319 printing inks (toner, inkjet, offset, and Intaglio) were analyzed directly on the paper substrate using scanning electron microscopy‐energy dispersive spectroscopy (SEM‐EDS) and Laser Ablation‐Inductively Coupled Plasma‐Mass Spectrometry (LA‐ICP‐MS). As anticipated, the high sensitivity of LA‐ICP‐MS pairwise comparisons resulted in excellent discrimination (average of ~ 99.6%) between different ink samples from each of the four ink types and almost 100% correct associations between ink samples known to originate from the same source. SEM‐EDS analysis also resulted in very good discrimination for different toner and intaglio inks (>97%) and 100% correct association for samples from the same source. SEM‐EDS provided complementary information to LA‐ICP‐MS for certain ink types but showed limited utility for the discrimination of inkjet and offset inks.     

Differentiation of blue ballpoint pen inks by positive and negative mode LDI-MS

Usually, the differentiation of inks on questioned documents is carried out by optical methods and thin layer chromatography (TLC). Therefore, spectrometric methods were also proposed in forensic literature for the analysis of dyes. Between these techniques, laser desorption/ionization mass spectrometry (LDI-MS) has demonstrated a great versatility thanks to its sensitivity to blue ballpoint ink dyes and minimal sample destruction. Previous researches concentrated mostly on the LDI-MS positive mode and have shown that this analytical tool offers higher discrimination power than high performance TLC (HPTLC) for the differentiation of blue ballpoint inks. Although LDI-MS negative mode has already been applied in numerous forensic domains like the studies of works of art, automotive paints or rollerball pens, its potential for the discrimination of ballpoint pens was never studied before. The aim of the present paper is therefore to evaluate its potential for the discrimination of blue ballpoint inks. After optimization of the method, ink entries from 33 blue ballpoint pens were analyzed directly on paper in both positive and negative modes by LDI-MS. Several cationic and anionic ink components were identified in inks; therefore, pens were classified and compared according to their formulations. Results show that additional information provided by anionic dyes and pigments significantly increases the discrimination power of positive mode. In fact, it was demonstrated that classifications obtained by the two modes were, to some extent, complementary (i.e., inks with specific cationic dyes not necessarily contained the same anionic components).     

Classification algorithm using halftone features of counterfeit bills and CNN

With recent advancements in image processing and printing technology, home printers have improved in performance and grown more widespread. As such, they have been increasingly used in counterfeiting and forgery. Most counterfeit bills in Korea have been created using home scanners and printers. The identification of printer model is thus necessary to rapidly track down criminals and solve crimes. Household printers can be largely divided into inkjet and laser printers. These two types of printers print halftone textures instead of continuous images. This study proposed a technique of printer classification based on halftone textures that can be observed in printed documents. Since halftone textures are expressed as periodic lattices, the images were transformed via FFT, which is highly effective at expressing periodicity. ResNet, known for its superior gradient flow, was used for training. The experiment was conducted on 12 color laser jets and 2 inkjets. Scans of bills printed by each printer were used, and halftone texture analysis was performed on these images for printer model classification. Each image was cropped into several parts; one of the cropped parts was analyzed. The analysis showed that laser printers could be 100% distinguished from inkjet printers. An accuracy of 98.44% was achieved in make classification. When 50 cropped images were used instead of a single image, the technique achieved 100% accuracy in model classification. The proposed technique is non-destructive; it offers high accessibility and efficiency as it can be performed using a scanner alone, without requiring additional optical equipment.     

Differentiation of coloured inks of inkjet printer cartridges by thin layer chromatography and high performance liquid chromatography

Document examiners are frequently asked to determine whether or not a colour printout has originated from a particular inkjet printer. The printer can rarely be identified unless some unique defects or irregularities of the printer are present on the printout. However, it is possible to decipher the make and/or model of the printer by comparing the ink-profile of the questioned printout with that of a seized inkjet printer cartridge or from one in a database. This paper presents an overview of a systematic approach to characterising and discriminating the inks of different inkjet printer cartridges using thin layer chromatography (TLC) and high pressure liquid chromatography (HPLC) with multi-wavelength ultra-violet/visible (UV/Vis) detection. Ink samples from 23 different inkjet printer cartridges (including originals and substitutes) of different brands and colour printouts, printed by known printers were examined with newly developed chromatographic methods. Subsequently, a database of the ink-profiles was generated. The methods provide a useful tool for discriminating coloured inks in inkjet printer cartridges of different brands.     

针式打印文件检验的探讨

针式打印机是一种常用的办公机具,从针式打印机的结构和打印原理出发,阐述了针式打印文件种类鉴别和个体识别所依据的打印特征,为针式打印文件的检验鉴定进行操作层面的探讨。     

利用彩色文件上的图文特征鉴别喷墨打印机品牌

目的通过彩色文件上的图文特征鉴别喷墨打印机的品牌。方法在体视显微镜下观察采用不同喷墨机理的惠普、佳能和爱普生三大品牌喷墨打印机打印的彩色图文。结果通过对彩色图文上六种墨迹形态特征的比较,发现三大品牌喷墨打印机打印的彩色图文存在明显差异。结论依据这六种特征对三大品牌的喷墨打印机进行鉴别。     

An Examination of the Sequence of Intersecting Seal and Laser Printing Toner Line

Examining the sequence of intersecting seal and laser printing line is a significant method of determining the authenticity and validity of documents. In this study, five brands of stamp pad inks, three types of inkpads and seven kinds of laser printers were used to make heterogeneous line intersections. Observation method of physical characteristics, scraping technique and fluorescence method was used to determine the sequence of intersecting lines. Distinguishing features were noted between the materials produced in both sequences. As the results obtained from the study were positive, these features might provide a scientific basis for accurately determining the sequence between laser printing line and inkpad (stamp pad ink) seal.     

The forensic analysis of thermal transfer printing

Thermal transfer printing refers to printing processes that utilize heat to produce an image by either physical or chemical means or by a combination of both. As the technology has improved and the supplies have become less expensive, the use of thermal printing in the personal and business markets has increased significantly. Specifically, dye diffusion thermal transfer and thermal mass transfer have become predominant in the production of counterfeit credit cards, drivers' licenses, and other types of documents produced on plastic media. Chemical analysis by means of thin layer chromatography (TLC) has proven to be useful in characterizing various types of inks (e.g., writing and inkjet inks). In this study, the authors examined 81 different samples that included a total of 54 printer samples (43 photographic prints on paper and eleven plastic card samples) and 27 printer ribbons. A new TLC method was developed and tested utilizing a solvent system (80% n-hexane, 3% methyl ethyl ketone, and 17% ethyl acetate) that is capable of producing excellent resolution.     

Examination of spur marks found on inkjet-printed documents

In this paper, we propose the examination of spur mark evidence on inkjet-printed documents. Spur marks are tool marks created by the spur gears in the paper conveyance system of many inkjet printers. The relationship between printouts and printers were investigated by comparing the spur marks found on printed documents with reference spur marks sampled from known printers. The comparison was based on two characteristics of spur marks: pitch and mutual distance. These characteristics extracted the geometric features of spur marks and provided information on the type of spur gears and their location in the paper conveyance system. The spur marks on a printout matched the reference spur marks within three percent of the measured values. Spur marks were considered to be effective class characteristics to identify certain brands of inkjet printers since spur gears are used in many types of these machines.     

HPLC analysis of ballpoint pen inks stored at different light conditions

A method for comparison of ink entries on documents stored in different light conditions is presented. Various blue inks were exposed to light, both daylight and artificial light from fluorescent tubes. Inks were then extracted from the document and analyzed by HPLC (high performance liquid chromatography). Significant changes in composition were noted on exposure to light. These changes were followed by using ternary diagrams constructed for dyes generally present in blue-colored inks--Crystal Violet, Methyl Violet, and Tetramethyl Para Rosaniline. Also, the amount of the various compounds formed by decomposition of these dyes on exposure to light was measured and employed for comparison of inks. An example of the use of the proposed method in casework is given.     

Characterization of Printing Inks Using DART‐Q‐TOF‐MS and Attenuated Total Reflectance (ATR) FTIR

The rise in improved and widely accessible printing technology has resulted in an interest to develop rapid and minimally destructive chemical analytical techniques that can characterize printing inks for forensic document analysis. Chemical characterization of printing inks allows for both discrimination of inks originating from different sources and the association of inks originating from the same source. Direct analysis in real‐time mass spectrometry (DART‐MS) and attenuated total reflectance Fourier transform infrared spectroscopy (ATR‐FTIR) were used in tandem to analyze four different classes of printing inks: inkjets, toners, offset, and intaglio. A total of 319 samples or ~ 80 samples from each class were analyzed directly on a paper substrate using the two methods. DART‐MS was found to characterize the semi‐volatile polymeric vehicle components, while ATR‐FTIR provided chemical information associated with the bulk components of these inks. Complimentary data results in improved discrimination when both techniques are used in succession resulting in >96% discrimination for all toners, 95% for all inkjets, >92% for all offset, and >54% for all intaglio inks.