显微分光光度法检验蓝黑墨水字迹形成时间的适用性研究

本文利用显微分光光度法对八种不同品牌的蓝黑墨水字迹随时间变化的规律进行了研究,目的是考察该方法在鉴定蓝黑墨水字迹形成时间方面的适用性。实验分析了自然老化条件下的蓝黑墨水字迹在300~700nm波长范围内的反射光谱曲线,并计算墨迹与纸张的色差(△E),考查了△E与字迹形成时间的相关性,结果表明利用显微分光光度法测定蓝黑墨水字迹形成时间具有一定可行性。     

TDS-GC/MS法检测黑色中性笔墨迹中挥发性溶剂的历时性变化

目的应用热脱附-气相色谱/质谱(TDS-GC/MS)分析,研究7支黑色中性笔墨迹中挥发性溶剂的历时性变化规律。方法选取7支不同品牌的黑色中性笔,分别在A4纸和笔记本上进行一次制样,然后在不同时间点取样,应用所建TDS-GC/MS方法分析墨迹中乙二醇、二甘醇和三甘醇在200余天内的含量变化。结果6支笔中的乙二醇、三甘醇的含量在2个月之内有明显的下降,另1支笔中二甘醇的含量在5个月内还能观察到较明显的下降。目标物的历时性变化趋势能拟合成幂函数或对数函数。不同的纸张、不同的墨水对检测结果均有影响。结论黑色中性笔墨迹中的挥发性溶剂的含量随时间增加而下降,应用所建TDS-GC/MS方法,能为判断需检墨迹是否处于溶剂含量明显变化的阶段提供依据。     

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。     

紫外-可见光谱法研究蓝色圆珠笔色痕自然老化规律

目的论述自然老化下蓝色圆珠笔色痕中染料成分的变化规律。方法利用UV-VIS光谱对圆珠笔文字色痕中染料成分相对于铜酞菁的变化进行实验。结果得到染料与铜酞菁吸光度之比随老化时间变化的数据和曲线。结论利用UV-Vis光谱研究文件制成时间是可行的,为书写时间的鉴定拓展了思路。     

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。     

突触体素在弥漫性脑损伤后的表达水平变化

目的根据突触体素在脑损伤后的变化规律,研究其与弥漫性脑损伤后损伤时间之间的关系。方法垂直撞击SD大鼠造成脑损伤模型,在不同时间点处死大鼠,取脑组织冠状断面进行突触体素染色,将染色结果进行灰度值测定,并用SPSS软件对灰度值进行分析,从而推断损伤后随时间变化的突触体素变化情况。结果突触体素在损伤后一段时间内,随时间的变化呈现双拐曲线,显示突触体素表达与脑损伤及其修复过程密切相关。结论根据脑组织内突触体素的含量变化在一定范围内可以用于推断脑损伤时间。     

多次测定法确定蓝色圆珠笔字迹形成时间

通过研究相隔一定时间的多次测定数据的变化规律与书写时间的内在关系，建立了部分近期书写的圆珠笔字迹形成时间的检验方法，确定了相隔一定时间的两次测定数据的变化规律与书写时间内在关系的判定阀值。形成了无需对照样本即可判定部分圆珠笔字迹是否近期书写的检验方法。     

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”.     

组织细胞DNA含量变化与死亡时间的相关性研究

目的研究人死后各器官组织细胞DNA降解变化规律,探讨其在推断死亡时间方面的应用价值,为推断死亡时间提供科学依据。方法已知死亡时间人尸体的心、肝、脾、肾,按死后6,12,24和48h四个时间段取材,制成石蜡切片,经Feulgen染色并图像分析;同时将各器官组织按不同时间段取材,制成单细胞悬液,应用流式细胞仪检测DNA含量。结果(1)人体各器官组织细胞经FCM检测,脾细胞核DNA随死亡时间延长呈现较好的下降梯度,而心、肝、肾,则由于自溶较快,死后6h细胞核DNA含量已很低,其变化情况与死亡时间的相关性不佳;(2)各器官组织细胞核DNA染色强度指数均随死亡时间的延长而下降。结论(1)机体死亡后,各器官组织细胞核DNA含量随死亡时间延长逐渐减少,具有一定的变化规律,其中以脾细胞核DNA含量的变化趋势与死亡时间最具相关性,肝、肾次之,而心最差;(2)方法学分析,图像分析技术(IAT)与流式细胞术(FCM)两种检测方法在研究组织细胞DNA含量变化方面,各有利弊,可互补不足。     

GC Analysis of Black Gel Pen Ink Stored under Different Conditions

In many criminal and civil cases in China, the most commonly questioned documents are those written with gel pen ink. An important task for forensic document examiners is to identify whether two or more ink entries in one or more documents were written with the same ink type. The identification of the age of gel ink entries made poses an important and difficult problem for forensic document examiners. In this paper, the volatile components of gel ink were determined and the gel ink was classified by gas chromatography with a flame ionization detector. Calibration curves were created to express the relationship between the content of volatile gel ink components and the age of gel ink entries stored under natural and UV‐induced aging conditions. The correspondence between the natural and UV‐induced aging conditions was also established. The experimental results showed that GC was useful in the analysis of black gel ink and applicable for determining the relative age of gel ink entries under certain conditions.     

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.     

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.     

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.     

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.     

Ink dating,part I: Statistical distribution of selected ageing parameters in a ballpoint inks reference population

The development of ink dating methods requires an important amount of work in order to be reliably applicable in practice. Major tasks include the definition of ageing parameters to monitor ink ageing. An adequate parameter should ideally fulfil the following criteria: it should evolve as a function of time in a monotonic way, be measurable in a majority of ink entries, be as accurate and reproducible as possible, and finally it should not be influenced too much by transfer and storage conditions. This work aimed at evaluating the potential of seven ageing parameters for ink dating purposes: the phenoxyethanol quantity, relative peak areas (RPA), three solvent loss ratios (R%, R%*, NR%) and two solvent loss parameters (R_NORM, NR_NORM). These were calculated over approximately one year for 25 inks selected from a large database to represent different ageing behaviours. Ink entries were analysed using liquid extraction followed by GC/MS analysis. Results showed that natural ageing parameters (NR% and NR_NORM) were not suitable ageing parameters for ink entries older than a few weeks. RPA used other compounds present in ink formulations in combination to PE in order to normalise the results. However, it presented particular difficulties as they could not be defined for all inks and were thus applicable only for 64% of the studied inks. Finally, the PE quantity, R% and R_NORM allowed to follow the ageing of the selected inks over the whole time frame and were identified as the most promising. These were thus selected to test three different interpretation models in the second part of this article. The possibilities and limitations of ink dating methods will be discussed in a legal perspective.     

自动消色笔书写笔迹显现方法的实验研究

目的为自动消色笔书写笔迹的显现识别提供最佳方法。方法通过观察不同种类的自动消色笔书写在不同纸张上,保存在不同环境下的笔迹的消色过程、消色时间,分析判断消色笔书写笔迹的基本特性。使用文检仪、静电压痕仪、不同浓度的氢氧化钠溶液显现消色笔迹,比较不同显现识别方法的特点及优劣。结果不同的显现方法各有优劣,使用氢氧化钠溶液显色效果的最佳浓度为1.0 mol。结论在自动消色笔书写笔迹的显现中,可以根据不同情况,选择合适的显现方法达到识别检验的目的。     

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).