A study to investigate the evidential value of blue and black ballpoint pen inks in Australia

The aim of this project was to investigate the evidential value of blue and black ballpoint pen inks in Australia. For this purpose, 49 blue and 42 black ballpoint pen inks, of different brands, models and batches, representative of those ballpoint pens available on the Australian market at the time of the study, were analysed by three techniques: filtered light examination (FLE); reflectance visible microspectrophotometry (MSP); and thin-layer chromatography (TLC). The results showed that the power of the individual techniques to discriminate inks between and within brands, models and batches varied, the most informative techniques being TLC>FLE>MSP. The greatest degree of differentiation was achieved when using a combined sequence of techniques, the discriminating power being 0.99 and close to 1 for blue and black inks, respectively (different brands and models). In respect to the discrimination between different batches of a same brand and model, it was shown that 14 out of the 33 pairs compared could be discriminated. Overall, this study confirmed the high value of the examination of inks when applied to ballpoint pens available in Australia, especially when a combined sequence of techniques is applied.     

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。     

Raman spectroscopy of blue gel pen inks

Raman spectroscopy is becoming a tool of major importance in forensic science. It is a non-invasive, non-destructive analytical method allowing samples to be examined without any preparation. This paper demonstrates the use of the technique as a general tool for gel pen inks analysis. For this purpose, 55 blue gel pen inks, of different brands and models representative of gel pen available on the world market at the time of this study, were collected. A preliminary solubility test in methanol allowed separating them into two classes: 19 dye-based and 36 pigment-based gel inks. The latter were analysed by Raman spectroscopy (RS) using two wavelength laser sources (514.5 and 830 nm). Two main pigments were identified, pigment blue 15 and pigment violet 23.     

Hyperspectral imaging of gel pen inks: An emerging tool in document analysis

Hyperspectral imaging (HSI) is a useful technique in the examination of writing inks, including gel pen inks, which combines digital imaging with % reflectance spectroscopy. This facilitates the detection of subtle differences between chemically similar inks. This study analysed a variety of blue, red and black gel inks on white office paper using HSI. The potential of the technique for ink discrimination compared to other analytical methods of examination is highlighted. Discriminating powers of 1.00, 0.90 and 0.40 were achieved using HSI for red, blue and black gel inks respectively. The overall discriminating power of 0.76 for the technique combined with its non-destructive nature and minimal sampling requirements demonstrates promise for this type of application.     

Forensic discrimination of blue ballpoint pen inks based on thin layer chromatography and image analysis

This article aims to provide a new and fast method for differentiation of inks on a questioned document. The data acquisition was carried out by designing specific image analysis software for evaluating thin layer chromatograms (TLC-IA). The ink spot was extracted from the document using methanol and separated by TLC using plastic sheet silica gel 60 without fluorescent indicator, and a mixture of ethyl acetate, ethanol, and water (70:35:30, v/v/v) as mobile phase. To discriminate between different pen inks, new software was designed on the basis of intensity profile of red, green, and blue (RGB) characteristic. In practice, after development of chromatogram, the chromatograms were scanned by ordinary office scanner, intensity profiles of RGB characteristics on the development straight of each sample were produced and compared with the mentioned software. RGB profiles of ballpoint inks from various manufacturers showed that the patterns in most cases were distinctly different from each other. This new method allowed discriminating among different pen inks with a high reliability and the discriminating power of 92.8%. Blue ballpoint pen inks of 41 different samples available on the local market were successfully analyzed and discriminated.     

A statistical methodology for the comparison of blue gel pen inks analyzed by laser desorption/ionization mass spectrometry

A statistical methodology for the objective comparison of LDI-MS mass spectra of blue gel pen inks was evaluated. Thirty-three blue gel pen inks previously studied by RAMAN were analyzed directly on the paper using both positive and negative mode. The obtained mass spectra were first compared using relative areas of selected peaks using the Pearson correlation coefficient and the Euclidean distance. Intra-variability among results from one ink and inter-variability between results from different inks were compared in order to choose a differentiation threshold minimizing the rate of false negative (i.e. avoiding false differentiation of the inks). This yielded a discriminating power of up to 77% for analysis made in the negative mode. The whole mass spectra were then compared using the same methodology, allowing for a better DP in the negative mode of 92% using the Pearson correlation on standardized data. The positive mode results generally yielded a lower differential power (DP) than the negative mode due to a higher intra-variability compared to the inter-variability in the mass spectra of the ink samples.     

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 the micro-FTIR spectroscopy, Raman spectroscopy and XRF method examination of inks

In routine examination of inks on questioned documents non-destructive analytical methods, such as microscopic and optical techniques are applied first. However, they are often insufficient to identify the inks used for the preparation of the document. In such cases, it is necessary to apply chemical methods that normally cause partial destruction of the examined material. The aim of this work was to evaluate the possibility of discrimination between inks by the use of spectrometric methods, i.e. micro-FTIR spectroscopy, Raman spectroscopy and XRF. About 70 samples of blue and black ballpoint pen and gel inks were examined. It was found that about 90% of the samples of the same type and colour could be distinguished using these methods.     

基于银胶表面增强拉曼光谱检验蓝色书写字迹初探

目的用基于银胶的表面增强拉曼光谱技术检验蓝色签字笔字迹。方法取4种常见不同牌号的蓝色签字笔在其字迹上滴加微量银胶,用显微共焦拉曼光谱仪进行检验。结果不同品牌的蓝色签字笔字迹的表面增强拉曼光谱不同。结论基于银胶的表面增强拉曼光谱技术可用于纸张上蓝色签字笔字迹的检验。     

光谱成像检验同种同色涂抹掩盖字迹研究

目的建立一种无损、灵敏、直观的同种同色涂抹掩盖字迹的显现方法。方法依据涂抹掩盖字迹油墨物质的同色异谱特征,利用可见光滤波型多光谱成像检验系统进行检验。结果黑色圆珠笔、蓝色圆珠笔、黑色签字笔和蓝色签字笔相互涂抹掩盖形成的同种同色涂抹掩盖样本,利用可见光滤波型多光谱成像检验系统进行检验,显效率分别为90.5%、69.1%、49.5%、78.6%,显现效果良好。结论多光谱成像技术可以显现同种同色涂抹掩盖字迹,且具有良好的显现效果。     

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).     

Identification of colorants in pigmented pen inks by laser desorption mass spectrometry

Pigments are rapidly replacing dyes as colorants in pen and printer inks, due to their superior colors and stability. Unfortunately, tools commonly used in questioned document examination for analyzing pen inks, such as TLC, cannot be used for the analysis of insoluble pigments on paper. Laser desorption mass spectrometry is demonstrated here as a tool for analyzing pigment-based pen inks. A pulsed nitrogen laser can be focused onto a pen stroke from a pigmented ink pen on paper, and positive and negative ions representative of the pigment can be generated for subsequent mass spectrometric analysis. Targeted pens for this work were a set of Uni-ball 207 pigmented ink pens containing blue, light blue, orange, green, violet, red, pink, and black inks. Copper phthalocyanine was identified as the pigment used to make both blue inks. A mixture of halogenated copper phthalocyanines were identified in the green ink. Unexpectedly, the pink ink was found to contain a red pigment, Pigment Red 12, treated with a mixture of water-soluble dyes. Each sample yielded ions representative of the pigments present.     

Experimental Research on Class Identification with a New Type of Erasable Gel Pens

A new type of erasable gel pen ink is becoming increasingly popular because of the modifiable characteristics for writing on documents. This study attempts to distinguish 12 types of blue and black erasable gel pens produced by mainstream stationery manufacturers using infrared (IR) visual analysis, Fourier transform infrared (FTIR) analysis, fluorescence analysis, and microspectrophotometry. The results demonstrate that IR visual, FTIR, and fluorescence analysis can be used to help distinguish each type of erasable gel ink. While microspectrophotometry can be used to effectively differentiate the blue gel inks in this study, there are limitations with respect to distinguishing black erasable gel pens. When these four optical analyses methods were used in combination, the gel inks could be accurately distinguished.     

Quantitative evaluation of europium in blue ballpoint pen inks/offset printing inks tagged with europium thenoyltrifluoroacetonate by spectrofluorometry and ICP-AES

Tagging of writing/printing inks with suitable inorganic taggants such as rare-earth chelates has the potential to help document examiners identify fraud in sensitive written/printed documents. Selection of rare-earth chelates as taggants primarily depends on the satisfactory sensitivity of analytical determination and the absence of the taggants in normal varieties of inks used for document writing/printing. Spectrofluorometric determination of trace amounts of europium in blue ballpoint pen inks and offset printing inks tagged with europium thenoyltrifluoroacetonate was carried out with sodium tungstate solution. Sodium tungstate acts as a specific reagent that enhances the fluorescence intensity of the Eu3+ ion. The excitation and emission wavelengths are 270 nm and 605 nm respectively. The results were compared with the data obtained with ICP-AES. Satisfactory recoveries were observed with precision better than 5% RSD and comparable accuracy. Under the optimized experimental conditions, detection limits and quantitation limits were determined. The detection limits obtained by spectrofluorometry and ICP-AES were 0.01 microg/mL and 0.006 microg/mL respectively whereas the limits of quantitation were about 0.03 microg/mL and 0.018 microg/mL respectively. The spectrofluorometric method is rapid, selective, sensitive and accurate for the determination of europium in blue ballpoint pen ink and offset printing inks and may be suitable for application in the examination of sensitive documents to aid in document related crime investigation. The advantages and limitations of the tagging approach and proposed analytical techniques are discussed.     

墨水书写时间测定的进展

本文追述了从20世纪20年代初到90年代末书写墨水的时间测定的进展.这包括,介绍新检验方法建立所需遵循的基本要求;推荐目前案件检验的工作程序,即墨水种类的确定,可疑文件的外观检验,同牌号、同配方、同批号比对样本的寻找;评述目前已为办案使用的各种书写年代测定的方法,如扩散法,转印法,染料比值法,气相色谱法、溶剂萃取法,差示扫描量热法等;以及讨论了有望用于年代测定的一些新技术,如用于钢笔墨水的电化学法,光谱法和用于圆珠笔墨水的显微分光光度法,付里叶变换拉曼光谱法等.     

蓝色圆珠笔字迹色痕FT-IR光谱经时变化的研究

笔者曾用FT-IR光谱法对108种不同蓝色圆珠笔油墨进行了系统分析,确定了油墨组成成份,实现了种类认定.在此基础上,选取了二种不同种类的蓝色圆珠笔油墨字迹色痕,在紫外光下定时照射,根据各自光谱特征峰校正峰高的计算,确定相关峰的相对峰高比.根据相对峰高比值随时间变化的规律,进行了曲线拟合和计算机编程.同时,探讨了油墨组份之间随光照时间的变化,其目的是为了推断字迹色痕的“年龄”.     

Application of Video Spectral Comparator (absorption spectra) for establishing the chronological order of intersecting printed strokes and writing pen strokes

The sequence of intersecting strokes of laser printers (black, blue, red and green) and typewriter ink (black) with the strokes of gel pen ink, ballpoint pen ink and fountain pen ink (black, blue, red and green) has been determined by studying their absorption spectra. The absorption spectra have been generated for each of the two pure inks (i.e. A and B) and points of their intersections (i.e. A over B and B over A) by using Video Spectral Comparator (VSC-2000-HR). The study was carried out with an assumption that the peak characteristics of spectra from the point of intersection should correspond to the peak characteristics of pure ink which was executed later. It was observed that the absorption spectrum of intersection corresponds with either the laser printer or the typewriter ink stroke, whether these strokes were executed earlier or later than the writing instrument strokes. As the results obtained from the study were negative, the FDEs are advised against the practice of this technique in the examination of the sequence of intersecting strokes for these specified inks.     

Evaluation of principal components analysis with high-performance liquid chromatography and photodiode array detection for the forensic differentiation of ballpoint pen inks.

Inks from seven black and eight blue ballpoint pens were separated by a high-performance liquid chromatography (HPLC) method utilizing a photodiode array detection (PDA). A classifier flowchart was designed for the chromatographic data based on the presence or absence of certain peaks at different wavelengths to qualitatively discriminate between the inks. The same data were quantitatively classified by principal components analysis (PCA) to estimate the separation between a pair of classes of ink samples. It was found that the black ballpoint pen inks were discriminated satisfactorily utilizing two-dimensional data of the peak areas and retention times at the optimum wavelengths. The blue pens were discriminated by analyzing the chromatographic data at four different wavelengths simultaneously with a cross-validated PCA. The results of this study indicated that HPLC-PDA coupled with chemometrics could make a powerful discriminating tool for the forensic chemist, especially when analyzing extensive and/or complex data.     

Statistical discrimination of black gel pen inks analysed by laser desorption/ionization mass spectrometry

Pearson correlation coefficients were applied for the objective comparison of 30 black gel pen inks analysed by laser desorption ionization mass spectrometry (LDI-MS). The mass spectra were obtained for ink lines directly on paper using positive and negative ion modes at several laser intensities. This methodology has the advantage of taking into account the reproducibility of the results as well as the variability between spectra of different pens. A differentiation threshold could thus be selected in order to avoid the risk of false differentiation. Combining results from positive and negative mode yielded a discriminating power up to 85%, which was better than the one obtained previously with other optical comparison methodologies. The technique also allowed discriminating between pens from the same brand.