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.     

Changes in composition of ballpoint pen inks on aging in darkness

A method for comparison of the relative age of ink entries written by the same ballpoint pen on documents stored in darkness is presented. Inks were extracted from the document and analyzed by HPLC (high performance liquid chromatography). On aging, changes in the chemical composition of the inks were noted. These changes were similar to those observed when inks were exposed to light or heat. The aging was followed by using ternary diagrams constructed for dyes generally present in blue-colored inks--Crystal Violet, Methyl Violet, and Tetramethyl Para Rosaniline. The procedure is applicable for relative dating of ink entries in diaries, notebooks, etc., where often several ink entries are written by the same ink. However, a prolonged exposure of the document to daylight and/or artificial light (light from fluorescent tubes) as well as to extensive heat will render the whole procedure inapplicable. An example of the use of the proposed method in casework is given.     

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.     

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”.     

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.     

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.     

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.     

Age determination of ballpoint pen ink by thermal desorption and gas chromatography-mass spectrometry

Two main approaches can be used for determining the age of an ink: indirect dating and direct dating. Indirect dating is based on the chemical analysis of an ink followed by comparison with known samples in a reference collection. The collection should contain information about the inks including the market introduction dates. This approach may allow for an anachronism to be detected. The second concept is based on measuring ink components that change with age. The analysis of solvents in ballpoint inks may be a useful parameter for determining the age of ink on paper. In a previous study, the authors demonstrated that thermal desorption of ink directly from paper, followed by chemical analysis using gas chromatography-mass spectrometry (GC-MS), is a promising procedure for characterizing ink-binder resins and solvents. Preliminary tests showed that monitoring the evaporation of ink solvent from ink on paper is not a suitable method for ink dating. Thermal analysis of ink on paper in two steps revealed that fresh ink releases a relative amount of solvent at a certain low temperature in a defined period of time, which decreases as the ink ages. As a consequence, this relative amount of solvent released at a certain low temperature, and its decrease with time, can be used to estimate ink age. This age-dependent parameter was studied in 85 different inks ranging in age from 1 week to 1.5 years. It was found that some inks showed a significant decrease of this parameter up to an age of several months, and that the aging process can be monitored within this period. For other inks, however, the age-dependent parameter decreases relatively fast, e.g., within a few days, to a constant level, which can be too fast for casework. Based on these results, a general procedure for assessing the age of ballpoint pen inks on paper was developed.     

Preliminary Study on Determining the Sequence of Intersecting Lines by Fluorescence Technique

The determination of the sequence of intersecting lines is an important part of questioned document examinations. A fluorescence technique was used to determine the sequence of heterogeneous intersecting lines produced using inkpad ink, stamp‐pad ink, ballpoint pens, gel pens, fountain pens, colorants of carbon paper, photocopiers, laser printers, and inkjet printers. A SteREO Discovery.V20 equipped with the ZEN Blue Lite software was chosen to perform the tests.As the results obtained from the study were positive under most conditions, the fluorescence technique was found to be very successful in determining the sequence of intersecting lines from ballpoint pen, gel pen, fountain pen, photocopier, laser and inkjet printers, and inkpad inks. The method was also successful in determining the sequence of intersecting lines from ballpoint pen, photocopier, laser printer, and stamp‐pad inks under most conditions. The technique was not successful in determining the order of crossing lines blending together.     

Evaluation of laser desorption mass spectrometry and UV accelerated aging of dyes on paper as tools for the evaluation of a questioned document

Laser desorption mass spectrometry (LDMS) may be used for the detection and identification of dyes found in inks. Naturally-aged and artificially-aged blue and black ballpoint pen inks containing the cationic dye methyl violet were analyzed on paper. The average molecular weight of the dye sample was calculated from LD mass spectral data and plotted versus time. The resulting aging curves demonstrate that, as dye degradation increases, the average molecular weight of the dye decreases. Typical variables involved in ink aging, such as the type of paper and ink formulation, were investigated. Results show that these variables influence the rate of dye degradation. Furthermore, UV accelerated aging has been developed and tested as an alternative to thermal approaches.     

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.     

Analysis of Indian blue ballpoint pen inks tagged with rare-earth thenoyltrifluoroacetonates by inductively coupled plasma-mass spectrometry and instrumental neutron activation analysis

Characterization and assessment of inks on sensitive documents for absolute/relative age determination is the challenging forensic problem in spite of practical difficulties. Tagging of ballpoint pen ink with suitable taggant(s) is a unique method to come out with definitive inferences on the detection of forgery in documents written with ballpoint pens. Selection of a proper taggant primarily depends on sensitivity of analytical determination and their absence in normal varieties of ink used for document writing. Rare-earth elements, from all technical considerations can be potential taggant(s) for inks. To ensure more compatibility with ink, 13 rare-earth thenoyltrifluoroacetonate chelates were prepared and characterized. The ballpoint pen inks were tagged with rare-earth thenoyltrifluoroacetonate chelates individually at about 1-100 ppm level depending on sensitivity of element under suitable optimized experimental conditions and instrumental sensitivity. Aliquots of such tagged ink having varying amounts of taggants were analyzed by ICP-MS and INAA. Satisfactory recoveries and a good linear relationship of intensity (signal) against concentrations/amounts were observed. Under the optimized experimental conditions, the detection limits were worked out. This study of tagging metal ions in combination with ICP-MS and NAA as an analytical tool can allow to draw various combination options based on different rare-earth chelates as suitable materials for tagging of ballpoint pen inks for absolute/relative age determination to aid in document related crime examination. The advantages and limitations of proposed analytical techniques are discussed.     

Evaluation of desorption/ionization mass spectrometric methods in the forensic applications of the analysis of inks on paper.

Fast atom bombardment and laser desorption mass spectrometry (LDMS) provide molecular level information concerning an ink's composition. Two ink-jet printer inks, Ink A containing the cationic dye Methyl Violet 2B, and Ink B containing the anionic dye, Solvent Black, were studied. Both positive and negative ion detection modes of the mass spectrometer were used. LD may be used for the analysis of inks on paper. Once on paper, the ink's solvent system has evaporated, leaving mainly the dyes behind, which are detected using LDMS. An ink fades with time, indicating that the dyes are degrading. Preliminary results from an accelerated aging study of ballpoint pen ink using UV irradiation confirm that dye degradation products are formed. The degradation chemistry follows an oxidative demethylation process for which all products formed are detected using LDMS. Results suggest that LDMS may be developed to determine the relative age of inks.     

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.     

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 blue ballpoint pen inks by laser desorption ionization mass spectrometry and high-performance thin-layer chromatography

The differentiation of inks on a questioned document can highlight a fraudulent insertion and is usually carried out by optical comparison and thin-layer chromatography (TLC). Laser desorption ionization mass spectrometry (LDI-MS) may also be used for the analysis of dyes from ink. This analytical technique was compared with a standard method of high-performance TLC (HPTLC) according to their capacity to differentiate blue ballpoint inks. Ink entries on paper from 31 blue ballpoint pens have been analyzed and their dye ink formulations compared. The pens were classified into 26 classes by LDI-MS against 18 for HPTLC. LDI-MS proved to be a more powerful method for differentiating ink formulations because it provides information about dye structures (molecular weights) and relative quantification of dye classes (peak areas). Sample preparation was minimal and analysis time was short in contrast to the more complex extraction, application, and development steps of the HPTLC method. However, only basic dyes and pigments were identified using positive mode LDI-MS, while HPTLC did yield additional information about acid dyes.     

Differentiation of ballpoint pen inks by thermodesorption and gas chromatography-mass spectrometry

Differentiation and classification of ink entries with dated samples of a reference collection are important aspects in the examination of questioned documents. Classification of writing inks is presently achieved by analysis of dyes and colorants contained in the ink. This technique has its limitations in newly developed ink formulations with identical dye composition but differing in their solvents and binder resins. This paper introduces a method for the determination of solvents and binder resins of an ink sample directly from paper without sample preparation. This aim is accomplished by thermodesorption of the sample followed by gas chromatography/mass spectroscopy. The method was tested on numerous samples of ballpoint pen inks, which were subsequently grouped into several solvent and resin subgroups. A case study shows the applicability of the newly developed method.     

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。     

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.