基于气相色谱质谱法的不同极性圆珠笔墨迹的比较分析

目的采用气相色谱质谱法(GC/MS)比较分析不同极性圆珠笔墨迹的挥发性溶剂组成,探讨圆珠笔墨水溶剂成分的差异性。方法对书写墨迹采用甲醇超声提取离心后取上清液进样分析。气相色谱条件:HP-INNOWax色谱柱,分流比:3:1,程序升温:80℃保持1 min,15℃/min升温至150℃,保持1 min,6℃/min升温至250℃,保持5 min。质谱条件:EI离子源,溶剂延迟:3min,扫描范围为:29-350 amu。结果不同极性圆珠笔墨迹溶剂成分均为醇类物质,水性和中性圆珠笔墨水溶剂多为乙二醇、丙二醇和丙三醇等中等极性的脂肪醇,油性圆珠笔墨水多采用苯甲醇、苯氧乙醇等弱极性芳香醇作为常用有机溶剂。结论 GC-MS对圆珠笔墨迹的不同溶剂组成进行有效区分与识别,方法可行、结果可靠。     

薄层色谱法鉴别黑色中性笔色痕的种类

黑色中性笔墨水主要由溶剂、色料、增稠剂、稳定剂和其他添加剂等组成,不同厂家或同厂家不同牌号中性笔墨水的成分不同,尤其是色料差别较大,这为中性笔墨水的种类鉴别提供了依据。本文利用数理统计中的均匀设计法和正交设计法安排试验,建立了一种可用于黑色中性笔色痕种类鉴别的方法:用N,N-二甲基甲酰胺作为黑色中性笔色痕的提取剂,四氢呋喃:甲醇:1,2-二氯乙烷:氯仿=30:15:5:7为展开剂的薄层色谱分析法。     

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。     

中性笔笔痕特征稳定性的实验分析

在阐明中性笔特点的基础上,通过对3位书写人用5支中性笔书写的90份实验材料的放大观察与测量,探讨中性笔笔痕特征在书写速度、书写姿势、书写衬垫物软硬、纸张洇散程度以及书写笔新旧程度不同时笔痕特征稳定性的具体表现,并分析影响笔痕特征稳定性的主要因素及变化规律。掌握影响中性笔笔痕特征稳定性具体因素及其变化规律,是有效利用中性笔笔痕特征进行笔迹鉴定的重要前提。     

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。     

自制海洛因标准品在常用有机溶剂中稳定性研究

目的 研发海洛因标准品及优化分析方法,以对云南缴获海洛因样本提纯制备成的自制海洛因对照品在常用有机溶剂中的稳定性进一步研究.方法 采用内标及GC、GC/MS方法,通过对提纯制备的海洛因在5种有机溶剂中冷藏保存后含量的变化,观察海洛因在常用有机溶剂中的稳定性.结果 乙醇、三氯甲烷及乙腈为溶剂的自制海洛因对照品储备液,保存30天时间范围内海洛因含量未发生明显变化;以丙酮作为溶剂的自制海洛因对照品储备液,在7至30天时间范围内,海洛因含量明显升高;以甲醇作为溶剂的自制海洛因对照品储备液,在0小时至30天时间范围内,海洛因含量一直呈明显的下降趋势.结论 乙醇、三氯甲烷及乙腈可以作为海洛因样品储备液溶剂使用,丙酮、甲醇不适合作为海洛因样品储备液溶剂使用.     

裂解气相色谱-质谱对百元假币红色墨迹的初步研究

目的 初步建立鉴别百元假币的方法.方法 分别各取适量5张百元假币红色墨迹,应用裂解气相色谱-质谱法(Py-GC/MS)直接检测.结果 通过分析裂解产物,获得百元假币墨迹成膜物主要成分信息.结论 该研究结果可对目前社会上发现的5种百元假币红色墨迹的成膜物进行分析.     

烫染对头发中氟硝西泮和7-氨基氟硝西泮含量影响

目的建立头发中氟硝西泮和7-氨基氟硝西泮的LC-MS/MS定性定量分析方法,研究烫发和染发处理对头发中氟硝西泮和7-氨基氟硝西泮含量的影响。方法 86例阳性样本被分为未处理组和烫发或染发处理组,经甲醇超声提取后,采用LC-MS/MS检测,分析头发样本经烫发和染发前后氟硝西泮和7-氨基氟硝西泮的含量变化。结果烫发处理后氟硝西泮有87.50%未检出,85.19%的7-氨基氟硝西泮阳性样本中药物含量下降幅度超过50%;染发处理后氟硝西泮含量下降幅度为10.64%～36.11%,而7-氨基氟硝西泮阳性样本有66.67%的浓度升高,且幅度大于100%。结论烫发和染发可明显影响头发中氟硝西泮和7-氨基氟硝西泮的含量,在检测头发中氟硝西泮及其代谢物的含量时,应结合头发的颜色和状态作出综合分析。     

高效液相色谱-串联质谱法测定肝组织中华蟾酥毒基和酯蟾毒配基

目的建立灵敏、准确的高效液相色谱-串联质谱法(HPLC-MS/MS)测定肝组织中华蟾酥毒基和酯蟾毒配基含量的方法。方法肝组织匀浆液中加入内标地塞米松,用二氯甲烷提取后挥干,残渣加入甲醇溶液溶解并上样到ProElut C18固相萃取柱上分离净化,应用HPLC-MS/MS正离子多反应监测模式测定。结果肝组织中华蟾酥毒基和酯蟾毒配基分别在1~204 ng/g和1~206 ng/g范围内线性关系良好。检测限(S/N≥3)均为0.3 ng/g。基质效应为96.5%~126.7%。萃取回收率为70.0%~82.3%。日内及日间精密度均小于10%。结论所建方法灵敏、可靠,能满足法医毒物分析的鉴定需要。     

荧光法判断激光打印文件朱墨时序的研究

目的 建立荧光法判断激光打印文件朱墨时序的检验方法,并分析不同型号的激光打印机制成的文件与不同材质的印章印文的采墨时序的特征.方法 利用VSCS000文检仪和Photoshop软件,采用荧光法对激光打印文件与印章印文交叉部位的特征进行检验,并对不同型号的打印机制成文字与不同材质的印章印文交叉部位的荧光特征进行分析比对.结果 发现常出现的共性特征为:制成文字先墨后朱,交叉部位的黑色墨迹颜色变淡并可见紫色荧光;先末后墨,交叉部位常常出现黑色墨迹缺损的现象,在缺损处可见紫色荧光点.但也表现出其特有的特征.结论 不同型号的打印机制成的文件与不同材质的印章朱墨时序所表现出来的特征不尽相同,在具体案件鉴定中应进行综合判断.     

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.     

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.     

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.     

A GC/MS study of the drying of ballpoint pen ink on paper

The determination of the age of an ink entry from a questioned document is often an essential problem and a controversial issue in forensic sciences. Therefore, it is important to understand the aging process of the different components found in ink. The aim of this work was to study the drying process of ballpoint ink, characterised by the disappearance of volatile solvents from the ink entry. Phenoxyethanol is of particularly high interest as it is found in more than 80% of the blue ballpoint pens at different concentrations. Liquid extraction followed by splitless gas chromatography/mass spectrometry in the selected ion mode was used to measure the quantitative decrease of solvents from ink entries made with a blue Parker ballpoint pen. Quantities of ethoxyethoxyethanol, dipropylene glycol, phenoxyethanol and phenoxyethoxyethanol were studied in ink entries up to 1.5 years old, thus allowing to calculate aging curves for this particular pen. The low quantities of solvents (in the microgram range for a 1 cm ballpoint entry) were found to decrease quickly after deposition of the ink on paper through the competitive processes of evaporation and diffusion. Losses of up to 75% of solvents were observed after a few seconds. The amount of ethoxyethanol stopped decreasing after about 10 days (quantities reached the nanogram range for a 1 cm ballpoint entry), while the aging curves of dipropylene glycol, phenoxyethanol and phenoxyethoxyethanol level off considerably after 2 weeks. It was observed that ethoxyethanol, dipropylene glycol and phenoxyethanol can also migrate from one sheet of paper to another if placed close enough (e.g. in a book or a stack of papers), therefore contamination from fresh ink strokes from other paper sheets has to be taken into account for those solvents. In this paper we demonstrate that differentiation between fresh ink (<2 weeks) and older inks is possible under laboratory storage conditions. For real cases samples, more parameters have to be studied and other possible pathways have to be considered.     

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.     

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.     

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。     

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.     

Determination of Changes in Crystal Violet and Phenoxyethanol (Dating Ink)

Ink dating is a significant problem in terms of forensic science. Ballpoint pens are generally used as writing tools on the documents. Aging is determination of the changes in dyes and solvents in the composition of ink over time by analytical methods. The evaporation of the solvents from the paper surface is faster than the decomposition process of the dyes. In this study, in 2017, we were asked by the court to determine whether the texts on the suspicious pages of an agenda dated 1996 were written within 2 years or earlier. Phenoxyethanol and dyes were examined in the composition of all suspected ink samples. The results show the determination of both the decomposition process of the dyes and the evaporation process of phenoxyethanol in the aging of the document entries written by ballpoint pen.