Preliminary Studies on the Absorbance Ratio Method Used to Determining the Age of Stamp‐pad Ink Seal

Stamp‐pad ink seals are often placed on important documents, and determining the dating of stamp‐pad ink seal is important to assess the authenticity of a document. In this study, 20 different brands and types of stamp‐pad inks were classified by ultraviolet visible spectrophotometer. Six different brands and types of papers were classified by micro‐Fourier transform infrared spectrometer and visual spectral comparator 6000. Three different brands of stamp‐pad inks and two different types of paper were used to make diachronic samples of the seals. A method was employed to date the stamp‐pad seals by comparing absorbance ratios and inks of known age. Curves were created to show the relationship between the absorbance ratio of ink and the age of the seals. The experimental results showed that the absorbance ratio method was applicable for the relative dating of stamp‐pad ink seals in some cases where the seal was placed on the document within 10 weeks.     

Dating of Seals Produced with Stamp‐Pad Ink Using Gas Chromatography Method

Seals are often placed on important documents, and determining the date when a seal was affixed can be important to assess the authenticity of a document. In this study, thirty‐seven different brands of stamp‐pad inks and three different types of paper were used to make diachronic samples of the seals. The volatile components of stamp‐pad ink were determined, and the stamp‐pad ink was classified by gas chromatography with a flame ionization detector. Calibration curves were created to show the relationship between the content of volatile stamp‐pad ink components and the age of stamp‐pad ink entries stored under natural aging, UV‐induced aging, and heating aging conditions. The experimental results showed that GC was useful in the analysis of stamp‐pad ink and applicable for determining the relative age of stamp‐pad ink entries in some cases where the seal was placed on the document within 3 months.     

Dating of Iron Gall Ink Using the Dissolution‐Diffusion Method

In many criminal and civil cases, some questioned documents are written with iron gall ink. Determining the date when an iron gall ink entry was written can be important to assess the authenticity of a document. A dissolution‐diffusion method was successfully employed to draw aging curves of iron gall ink entries stored in controlled conditions over 40 months. Calibration curves were created to indicate the relationship between the average dissolution‐diffusion rate of ink components and the age of ink entries stored under natural aging conditions. As preliminary findings of this study, the mixed solution of dimethyl formamide (DMF) and anhydrous ethanol was suitable to dissolve the dye of iron gall ink strokes made at different time. It was also determined that brands of iron gall inks, types of paper, and thickness of iron gall ink strokes had varying impacts on estimating the dates of iron gall ink strokes.     

Dating of Inkpad Seals Using the Extraction Rate Method: Preliminary Findings

Inkpad seals are often placed on important documents, and determining the date when a seal was affixed can be important to assess the authenticity of a document. In this study, three different brands of inkpads and four different types of paper were used to make diachronic samples of the seals. A double‐solvent extraction method was employed to date the inkpad seals by comparing extraction rates with inks of known age. Cyclohexane was selected as a weak solvent, and chlorobenzene was selected as a strong solvent. After testing, curves were created to show the relationship between the extraction percentage of ink and the date of the seals. The experimental results showed that the extraction rate method was applicable for the relative dating of inkpad seals in some cases where the seal was placed on the document within 6 months.     

Dynamic of the ageing of ballpoint pen inks: quantification of phenoxyethanol by GC-MS.

The ageing process of some inks were studied to evaluate whether it is possible to date them. We used gas chromatography coupled with mass spectrometry to measure the evaporation of volatile components. The selected approach thus follows the disappearance of one ink volatile component (phenoxyethanol) as a function of time. The ink ageing curve represents the ratio of an evaporating compound to a stable compound of ink according to time. The results obtained are thus independent of the quantity of ink sampled for analysis. We obtained for two pens, containing two different inks, a curve highlighting an exponential decrease of the evaporating compound. By fitting these curves we determined the limitations of dating a ballpoint pen ink. Two distinct behaviours were observed in two distinct modes, the first called 'fast mode' and the second called 'slow mode'. In order to try to explain the phenomenon, the studies were based on solvent diffusion theory in complex matrix (such as polymer on varnish). Calculations from certain parameters showed an extremely fast evaporation of ink solvents, as well as varying behaviour depending on the paper used. The results showed that it is not possible to date ballpoint pen inks with this method in document examination casework.     

Age determination of ballpoint pen ink by thermal desorption and gas chromatography-mass spectrometry

Two main approaches can be used for determining the age of an ink: indirect dating and direct dating. Indirect dating is based on the chemical analysis of an ink followed by comparison with known samples in a reference collection. The collection should contain information about the inks including the market introduction dates. This approach may allow for an anachronism to be detected. The second concept is based on measuring ink components that change with age. The analysis of solvents in ballpoint inks may be a useful parameter for determining the age of ink on paper. In a previous study, the authors demonstrated that thermal desorption of ink directly from paper, followed by chemical analysis using gas chromatography-mass spectrometry (GC-MS), is a promising procedure for characterizing ink-binder resins and solvents. Preliminary tests showed that monitoring the evaporation of ink solvent from ink on paper is not a suitable method for ink dating. Thermal analysis of ink on paper in two steps revealed that fresh ink releases a relative amount of solvent at a certain low temperature in a defined period of time, which decreases as the ink ages. As a consequence, this relative amount of solvent released at a certain low temperature, and its decrease with time, can be used to estimate ink age. This age-dependent parameter was studied in 85 different inks ranging in age from 1 week to 1.5 years. It was found that some inks showed a significant decrease of this parameter up to an age of several months, and that the aging process can be monitored within this period. For other inks, however, the age-dependent parameter decreases relatively fast, e.g., within a few days, to a constant level, which can be too fast for casework. Based on these results, a general procedure for assessing the age of ballpoint pen inks on paper was developed.     

How Much Can a Forensic Laboratory Do to Discriminate Questioned Ink Entries?

Questioned document examiners are frequently required to determine whether the questioned ink entries on a document are written with the same ink, either for forged document identification or relative ink dating. How many methods are sufficient to discriminate potentially different inks? In this paper, 18 blue ballpoint inks were first nondestructively examined with a video spectral comparator. The ink entries were subsequently extracted with organic solvents for analysis of the volatile solvents and dyes by GC/MS, TLC, and LC‐MS/MS. The 18 ink samples were divided into 10, 9, 12, and 14 categories by these four methods, respectively. With the combined results, there were only two inks that remained indistinguishable, but they were further differentiated by microscopy. Therefore, to achieve effective discrimination of ballpoint ink entries, the authors suggest that a complete examination should include an analysis of their optical features, volatile solvents, and dyes as well as the ink quality.     

Determination of the sequence of intersecting lines from laser toner and seal ink by Fourier transform infrared microspectroscopy and scanning electron microscope / energy dispersive X-ray mapping

The aim of this study was to verify that the combination of Fourier transform infrared microspectroscopy and scanning electron microscope / energy dispersive X-ray mapping could be applied to line intersection problems. The spectral data of red seal ink, laser toner and their intersections, such as peak location and peak intensity, were described. Relative peak height ratios of different chemical components in intersecting lines were used to distinguish the sequences. Energy dispersive X-ray mapping characteristics of intersecting areas were also detailed. The results show that both the laser toner and the seal ink appear on the surface of intersections, regardless of the sequence. The distribution of the two inks on the surface is influenced not only by the sequence of heterogeneous lines but also by diffusion. Fourier transform infrared microspectroscopy and scanning electron microscope/energy dispersive X-ray mapping are able to explore the chemical components and the corresponding elemental distribution in the intersections. The combination of these two techniques has provided a reliable method for sequencing intersecting lines of red seal ink and laser toner, and more importantly, this method may be a basis for sequencing superimposed lines from other writing instruments.     

Characterization and dating of blue ballpoint pen inks using principal component analysis of UV-Vis absorption spectra, IR spectroscopy, and HPTLC

The ink of pens and ink extracted from lines on white photocopier paper of 10 blue ballpoint pens were subjected to ultraviolet-visible (UV-Vis) spectroscopy, infrared (IR), and high-performance thin-layer liquid chromatography (HPTLC). The R(f) values and color tones of the bands separated by thin-layer chromatography (TLC) analysis used to classify the writing inks into three groups. The principal component analysis (PCA) investigates the pen responsible for a piece of writing, and how time affects spectroscopy of written ink. PCA can differentiate between pen ink and ink line indicates the influence of solvent extraction process on the results. The PCA loadings are useful in individualization of a questioned ink from a database. The PCA of ink lines extracted at different times can be used to estimate the time at which a questioned document was written. The results proved that the UV-Vis spectra are effective tool to separate blue ballpoint pen ink in most cases rather than IR and HPTLC.     

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.     

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.     

防止茚三酮溶液扩散纸张字迹的研究

目的 解决茚三酮溶液在显现手印同时对纸张上字迹产生扩散作的问题;方法 分别采用茚三酮丙酮溶液,茚三酮氟利昂溶液,茚三酮石油谜溶液,茚三酮庚烷溶液作比较。结果 钢笔字迹用4种溶液均不易扩散;纸张上其它成份字迹用后两种方法显现手印时可有效保存纸张上文字原貌。     

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。     

Identification and dating of the fountain pen ink entries on documents by ion-pairing high-performance liquid chromatography

A novel approach for the identification and dating of the fountain pen ink entries on paper has been established by ion-pairing high-performance liquid chromatography (IP-HPLC). Twelve black and six red fountain inks have been collected, and their ink entries have been prepared by drawing lines on paper. The chromatographic conditions for separation of their dye components after extraction with solvents were optimized. Under the optimized conditions, the 18 fountain pen inks were differentiated individually by comparing the number of detectable main or minor dye components, and the relative peak intensities of each component. The ink entries were artificially and naturally aged, and the analysis results showed that the ink dye components were significantly decomposed when exposed to UV or fluorescent light compare to those of inks stored under natural condition. The changes of the relative peak height for the dye components were linearly related to the aging time, especially under natural aging conditions. The degradation characteristics of the dye components under different aging conditions provide scientific evidences for dating of the suspicious fountain pen ink entries on document.     

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.     

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.     

Prepared Disappearing Ink and Deciphering of Documents

Disappearing inks can be used for forgeries in many fields. In this study, thymolphthalein indicator solution was prepared as a disappearing ink. A total of 54 different solutions containing thymolphthalein were prepared at six different concentrations and nine different pH values. Among the prepared solutions, 0.16 g/50 mL and 0.32 g/65 mL thymolphthalein at pH 14 were the optimum solutions that were not distinguishable from regular ink when applied to promissory note. Fountain pens were filled with the abovementioned ink solutions and applied to promissory notes for experimental purposes. After 40 h, ink residues were not visible on promissory notes written with the ink with the optimum pH (pH = 14) value. To decipher the entries that disappeared, an instrumental method (Video Spectral Comparator‐8000) and a chemical method (using NH₃ vapor) were used, succeeded at 0.32 g/65 mL, but failed at 0.16 g/50 mL thymolphthalein. Therefore, NH₃ had to be sprayed for 0.16 g/50 mL with negligible harm.     

中性墨水笔墨迹中甘油成分的气相色谱分析及历时性变化初探

目的对中性墨水笔墨迹中甘油成分和随时间变化规律进行研究。方法利用气相色谱法分析了含有甘油溶剂成分的中性墨水笔字迹墨迹,并对甘油成分含量相差较大的字迹样本的变化规律进行了研究。结果得到了3种字迹墨迹中甘油成分随字迹形成时间变化的关系曲线。结论曲线变化规律表明,书写时间6个月的中性墨水笔墨迹中甘油成分的含量变化出现拐点,6个月以后甘油成分的含量基本趋于不变。     

Application of laser induced breakdown spectroscopy to examination of writing inks for forensic purposes

The research was focused on the analysis of writing inks using the laser induced breakdown spectroscopy (LIBS) technique. 34 samples of blue, 30 of black, and 21 of red writing inks were analyzed under optimized conditions to determine the variation of chemical composition of inks between different colours, brands and types. Nine elements (Ba, Cr, Cu, Fe, Li, Mo, Mn, Ni and W) were taken into account during comparative analysis of inks. Because of the strong effect of the paper spectrum, elements often found in inks (Ca, Al, Mg, Na, Ti, and Si) were eliminated from LIBS analysis of inks. It was determined that the LIBS method is capable of revealing qualitative elemental differences between ink samples. The discrimination power of this method was found to be 83, 82 and 61% for blue, black and red inks, respectively. Inks produced by the same producer were able to be differentiated in some cases. The results showed the potential of LIBS for forensic purposes as an effective and robust technique, requiring a small amount of sample and giving analytical information in a very short time.     

Characterization of ballpoint pen inks by thermal and desorption and gas chromatography-mass spectrometry

The characterization of ink on paper is of importance for dating and comparing questioned ink entries in forensic document examination. Inks are commonly characterized by their colorant profile that is identified by well-established analytical methods. Numerous ink formulations show identical colorant profiles, though. In order to differentiate inks that are not distinguishable by colorant analysis, a method for the characterization of colorless ink ingredients, namely binders, solvents and additives is necessary. In this paper, we propose a technique for the analysis of colorless compounds in ballpoint inks using direct thermal desorption of the ink on paper followed by chemical analysis of the desorbed volatile compounds by gas chromatography-mass spectrometry. As compared to liquid extraction and subsequent analysis of the extracts, the technique avoids possible contamination risks. Sensitivity is very high due to the enrichment of volatile components by thermal desorption. Even from old samples, the chromatograms obtained by the method enable the determination of binder polymers, solvents and additives. Pure binders as used by ink manufacturers were analyzed for unambiguous assignment of analytical results to specific polymers. To prove the practical applicability, we analyzed 121 ballpoint pens, not all having the same colorant profile, and grouped the pens into resin and solvent categories.