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 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.     

拉曼光谱成像技术检验朱墨时序中书写笔种类对检验结果的影响研究

目的考察在运用拉曼光谱阵列面扫描检验朱墨时序的方法中书写笔油墨种类对检验结果的影响。方法根据拉曼谱图的不同对搜集的188种书写笔（包括22种黑色圆珠笔,62种蓝色圆珠笔,62种黑色签字笔,42种蓝色签字笔）进行扫描并分类,采用拉曼光谱阵列面扫描技术对书写笔与同一印泥和印油形成的朱墨时序样本进行检验。结果 188种书写笔被分为4大类23小类,4类书写笔与印泥或印油形成的朱墨时序样本都得到了较好的检验结果。结论在本实验条件下,书写笔油墨种类对拉曼光谱阵列面扫描检验朱墨时序的检验结果没有影响。     

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.     

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.     

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.     

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.     

A study to investigate the evidential value of blue gel pen inks

The aim of this project was to investigate the evidential value of blue gel pen inks in Europe. For this purpose, 33 blue gel pen inks, of different brands and models, representative of those available on the European market at the time of the study, were analyzed using three techniques: filtered light examination (FLE), Raman Spectroscopy (RS), and scanning electron microscopy (SEM). First, after visual examination (naked eye and stereo microscope), it was possible to classify the 33 inks into three groups described as: milky, metallic, and normal. This paper describes in detail the results obtained for the normal gel pen group. The ability of the techniques to discriminate gel inks between and within brands varied. The results indicated that RS and SEM were more discriminating than FLE. The greatest degree of differentiation was achieved when using a combination of RS and SEM techniques (discriminating power = 0.91). This study also highlights some problems concerning the identification of the brand of a gel pen from a written text.     

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.     

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.     

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.     

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。     

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.     

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.     

Differentiation of black gel inks using optical and chemical techniques

Gel ink pens have become a common writing instrument in the United States. Questioned document examiners often attempt to optically differentiate gel inks from each other and from other non-ballpoint ink writings (e.g., those from roller-ball pens). Since early formulations were primarily pigment-based, they do not elute when analyzed by thin-layer chromatography. However, recent gel ink formulations (i.e., within the past five years) include dye-based inks that can be easily separated. This study differentiates black gel inks using optical and chemical techniques. The techniques include: microscopy, visible and near infrared reflectance, near infrared luminescence, thin-layer chromatography (TLC), spot tests, and gas chromatography/mass spectrometry (GC/MS). As a result of this study a flow chart has been developed allowing for a systematic determination of a questioned ink. In addition, an analysis of volatile compounds found in gel inks revealed that there are some unique ingredients that may be found in gel inks that are not typically found in other non-ballpoint inks.     

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.     

运用光谱成像技术区分同色棉纤维

目的研究同色棉纤维的检验方法。方法运用成像光谱法对红、蓝、黑3个颜色组的棉纤维进行区分。结果红色棉纤维的鉴别率为62．2％，蓝色棉纤维的鉴别率为77．8％，黑色棉纤维的鉴别率为69．6％。结论实验结果表明，光谱成像技术可以区分大部分同色棉纤维。拓宽了纤维检验的方法，解决了同色棉纤维的区分问题，该方法能够用于对微量同色棉纤维的快速鉴别。     

Effect of electron beam irradiation on forensic evidence. 2. Analysis of writing inks on porous surfaces

The effect of electron beam irradiation on a series of different writing inks is described. As the anthrax-tainted letters were discovered in October 2001, the U.S. government began to experiment with the use of the electron beam irradiation process for destroying such biological agents. Plans initially considered a large-scale countrywide use of this technology. However, over time the scope of this plan as well as the radiation dosage were reduced, especially when some adverse consequences to mailed items subjected to this process were observed. Little data existed at the time to characterize what level of damage might be expected to occur with common items sent through the mail. This was especially important to museums and other institutions that routinely ship valuable and historic items through the mail. Although the Smithsonian Institution initiated some studies of the effect of electron beam irradiation on archived materials, little data existed on the effect that this process would have on forensic evidence. Approximately 97 different black, blue, red, green, and yellow writing inks were selected. Writing ink types included ballpoint, gel, plastic/felt tip, and rollerball. All noncontrol samples were subjected to standard mail irradiation conditions used by the U.S. Postal Service at the time this experiment was performed. A video spectral comparator and thin-layer chromatography (TLC) analysis were used to evaluate both the control and the irradiated samples. Some published studies reported changes in the presence/absence of dye bands in the chromatograms of irradiated writing inks. Some of these studies report the formation of additional dye bands on the chromatogram while others report missing dye bands. However, using standard testing guidelines and procedures, none of the 97 irradiated inks tested were found to show any significant optical or chemical differences from the control samples. In addition, random testing of some of the ink samples using a second solvent system did not reveal any changes. However, one control ink did show some minor changes in optical properties and dye characteristics over time (but not TLC) while the irradiated sample remained stable. Significant changes in the ultraviolet fluorescence characteristics of the irradiated paper samples themselves (not inks) were also observed.