应用HPLC研究蓝色签字笔迹字迹色痕光老化规律

目的对蓝色签字笔所形成的字迹色痕光老化规律进行研究。方法比对14种蓝色签字笔样品在暗处保存条件下、自然光照射及强灯光照射等老化条件下物理特征变化情况;使用高效液相色谱法,监测蓝色签字笔墨水中色料成分的变化情况,并寻找蓝色签字笔墨水字迹自然光老化规律。结果强灯光照射后出现外观明显的老化现象,暗处存放的样本存在较长的老化时限。在自然光照射下30天内,样品色料成分的相对含量均随时间发生两个阶段的变化。结论样本字迹的外观为鉴定蓝色签字笔墨水字迹的形成时间提供了重要的信息。结合HPLC分析结果,可以确认字迹是否经过光照人工老化,为字迹形成时间鉴定的重要参考依据。     

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”.     

光照人工老化原子印油色痕的分析

通过高效液相色谱法对光照人工老化后的原子印章色痕中的主要组分——颜料与油脂进行分析。寻找研究这些组分随时间变化的规律。为原子印章色痕形成时间的深入研究提供条件。     

基于HPLC的三芳甲烷类染料字迹人为老化的实验研究

目的对蓝色圆珠笔字迹在经过紫外光源老化后的独特特征进行研究,建立确认紫外灯照射的人为老化文件的方法。方法本文以蓝色圆珠笔字迹为研究对象,蓝色圆珠笔中的三芳甲烷类染料在紫外灯的照射下会吸收光子的能量加速其老化脱甲基的反应,通过适当的假设可以推导出其老化程度随时间变化的老化方程,由于目前紫外灯管几乎全部是线型结构,建立合适的坐标系,假设线型灯管能量分布均匀,且紫外线以球面波的形式传播出去,可以计算出纸面上任意一点的能量,通过纸张表面不同位置的三芳甲烷类染料的老化程度的不同来区别自然老化文件与紫外灯人为老化文件的不同。结果经过实验发现对于紫外灯人为老化文件来说甲基紫初始含量比上老化后含量的对数值与紫外灯对于该点的能量的辐出的比值为一个常数K,该K值稳定,浮动范围小,线性关系的置信度大于99%,可以认为两个参数之间存在显著地线性关系,可以证明对于老化方程的推导和能量密度分布函数的推导合理符合实际,对于自然老化文件来说则不存在这种规律。结论可以利用这种特殊的分布规律构建一个衡量这种分布的函数来定量地确认紫外灯照射的人为老化文件。     

GC-HPLC法考察圆珠笔字迹油墨厚度对溶剂挥发速率的影响

目的考察圆珠笔字迹油墨厚度对溶剂挥发速率的影响。方法采用GC/HPLC联用技术对不同时间、不同字迹油墨厚度在同种纸张上的圆珠笔油墨字迹中的溶剂、染料成分的定量分析。结果字迹油墨较厚的苯甲醇、苯氧基乙醇的含量随时间的变化比字迹油墨较薄的慢。结论字迹油墨的厚度对溶剂的挥发速率影响较大。     

LC-MS/MS法检测圆珠笔墨迹中碱性蓝7及其去乙基产物的降解变化

目的考察圆珠笔墨迹中碱性蓝7及其去乙基产物的降解变化,为圆珠笔墨迹书写时间的研究提供基础数据。方法用氙灯老化碱性蓝7以生成其5个去乙基产物。建立LC-MS/MS检测碱性蓝7及其去乙基产物的方法。制作圆珠笔墨迹样本,在室内自然光照条件下老化3个月,同时进行控制实验条件的氙灯老化和高温老化实验。结果碱性蓝7的相对含量持续下降,其第一、第二级去乙基产物E4、E3的相对含量相继达到最大值,剩余三个去乙基产物E2、E1和E0的相对含量在三个月内持续增加。结论碱性蓝7的相对含量与光的辐照能量呈指数函数关系,其去乙基产物E4、E3的相对含量与光的辐照能量呈二次函数关系。不同油墨中碱性蓝7的老化曲线不同。温度对碱性蓝7的降解基本没有影响。     

拉曼光谱面扫描成像判断黑色圆珠笔交叉笔画书写先后顺序

目的建立一种灵敏、准确、无损的黑色圆珠笔交叉笔画书写顺序的检验方法。方法依据黑色圆珠笔油墨的同色异谱特征，利用显微共焦激光拉曼光谱仪进行面扫描成像分析检验。结果即使是差异很小的黑色圆珠笔油墨书写的交叉笔画，经过面扫描成像和图像处理后，也能看到先写笔道的连续性被后写笔道中断。结论拉曼光谱面扫描成像技术能有效判断黑色圆珠笔交叉笔画书写的先后顺序。     

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。     

签字笔与圆珠笔笔痕特征的比较研究

目的 探讨签字笔笔痕是否天然地适用圆珠笔笔痕检验条件而能够进行同一认定.方法 运用比较分析方法,在不同纸张条件下,以签字笔和圆珠笔为研究对象,收集288份有效实验样本,分别观察、记录、分析实验样本中的所产生的笔痕特征.结果 签字笔笔痕主要出现在大笔画的划痕特征；签字笔笔痕的稳定性和特定性要比圆珠笔弱.结论 签字笔笔痕同一认定需要考虑签字笔本身的特性,不可盲目鉴定.     

双溶剂提取法偏差范围的实验分析

目的双溶剂提取法是鉴定圆珠笔油墨字迹相对书写时间的方法之一,该方法简单有效,但在实际办案中发现,提取率的范围对数据的偏差范围有着直接影响。本文旨在通过实验分析偏差范围。方法通过对多种牌号的圆珠笔油墨新书写的字迹样本和自然老化样本进行平行实验。结果得到了不同提取率范围内的圆珠笔油墨提取率偏差范围。结论为双溶剂提取法鉴定圆珠笔油墨相对书写时间的界定提供了较为可靠的实验依据。     

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.     

Systematic analysis of bulk blue ballpoint pen ink by FTIR spectrometry

A classifying method on bulk blue ballpoint pen ink has been studied by Fourier transform infrared (FTIR) spectroscopy. By using this method, a total of 108 blue ink samples have been divided into two groups depending on their main component. Spectral characteristics of these inks such as frequency and absorbance are described by way of artificial intelligence of pattern recognition, and 35 subgroups from the 108 inks are distinguished by their correlation coefficient (lambda). Under heat or exposure to ultraviolet light a mode of change in the age of the inks has been obtained. This approach has provided a reliable and nondestructive method for the characterization of bulk ballpoint writing ink, and more importantly, it might be a basis for dating of the blue ballpoint pen ink.     

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.     

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).     

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.     

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.     

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.     

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.     

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.