Analysis Of Inks Research Articles

Advances ofcapillary electrophoresis in clinical and forensic analysis (1999-2000).

In this paper, capillary electrophoresis in clinical and forensic analysis is reviewed on the basis of the literature of 1999, 2000 and the first papers in 2001. An overview of progress relevant examples for each major field of application, namely (i) analysis of drug seizures, explosives residues, gunshot residues and inks, (ii) monitoring of drugs, endogenous small molecules and ions in biofluids and tissues, (iii) general screening for serum proteins and analysis of specific proteins (carbohydrate deficient transferrin, alpha1-antitrypsin, lipoproteins and hemoglobins) in biological fluids, and (iv) analysis of nucleic acids and oligonucleotides in biological samples, including oligonucleotide therapeutics, are presented.

Encyclopedia of forensic sciences

Encyclopedia of forensic sciences

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.

HPLC Analysis of Ballpoint Pen Inks Stored at Different Light Conditions

A method for comparison of ink entries on documents stored in different light conditions is presented. Various blue inks were exposed to light, both daylight and artificial light from fluorescent tubes. Inks were then extracted from the document and analyzed by HPLC (high performance liquid chromatography). Significant changes in composition were noted on exposure to light. These changes were followed by using ternary diagrams constructed for dyes generally present in blue-colored inks--Crystal Violet, Methyl Violet, and Tetramethyl Para Rosaniline. Also, the amount of the various compounds formed by decomposition of these dyes on exposure to light was measured and employed for comparison of inks. An example of the use of the proposed method in casework is given.

Using Raman spectroscopy to solve crime: inks, questioned documents and fraud.

Raman microscopy is becoming a tool of major importance in forensic analysis, particularly of drugs and explosives. It is a non-invasive, non-destructive chemical probe allowing samples to be examined in their entirety without any preparation. This paper demonstrates the use of the technique as a general tool for inks analysis. Furthermore, it addresses two important issues that historically have been extremely difficult for the professional document examiner, namely, comparison of black ballpoint inks and the chronological sequencing of crossed ink lines. We show that Raman can successfully distinguish between a representative sample of commercially available black ballpoint inks. This data has been converted into a database for future reference. A method for chronological sequencing of crossed ink lines has been developed using confocal Raman microscopy. Case study work has shown the feasibility of this approach.

Analysis of pigments and inks on oil paintings and historical manuscripts using total reflection x-ray fluorescence spectrometry

Old oil paintings and illuminated historical manuscripts are valuable objects of cultural heritage. Pigments and inks once used for these artefacts today allow insights of art historical or archaeological relevance. For their identification, a number of non-destructive spectroanalytical methods can be applied. This paper first gives a historical review and describes fundamentals of optical and x-ray fluorescence spectrometry including instrumentation and analytical characteristics. The variant of total reflection x-ray fluorescence (TXRF) is shown to be a highly convenient tool for the characterization of inorganic pigments and inks. Since only micro-samples are needed, a very gentle sampling technique can be applied. It consists of rubbing a dry cotton-wool bud (Q-tip) over the painted surface without causing any visible damage. Only a minute amount of a few micrograms is removed from the object, transferred to a glass carrier and analyzed by TXRF. Some remarkable examples of TXRF analysis of old paintings and illuminated manuscripts are given. Rather than emphasizing the analytical details, the archaeometric potential of the method is illustrated. Copyright © 2000 John Wiley & Sons, Ltd.

Analysis of pigments and inks on oil paintings and historical manuscripts using total reflection x‐ray fluorescence spectrometry

Analysis of pigments and inks on oil paintings and historical manuscripts using total reflection x‐ray fluorescence spectrometry

Analysis of Ballpoint Pen Inks by Field Desorption Mass Spectrometry

Abstract Destructive identification of ballpoint pen ink was performed using field desorption mass spectrometry (FDMS) to determine the basic dyes in ballpoint pen ink. Seven different brands of black, blue, and red ballpoint pen inks (total: 21 samples) were examined in this study. A 1-mm section was cut from an ink line drawn on paper and used as the sample. Extraction was performed with methanol. Analysis of each extract by FDMS showed the molecular ion peak of each dye and the black, blue, and red inks were then classified into 6, 6, and 6 types, respectively, based on the ions detected. The results indicated that it was possible to distinguish between manufacturers of ballpoint pens. This analysis of ballpoint pen inks was found to be effective and the method was applied to the analysis of an actual forensic sample.

Investigation of Ball Point Pen Inks by Capillary Electrophoresis (CE) with UV/Vis Absorbance and Laser Induced Fluorescence Detection and Particle Induced X-Ray Emission (PIXE)

Abstract In the process of examining fraudulent documents ink analysis is a small but important part of the operation of forensic laboratories. Systematic approaches to ink comparison and identification have been performed by optical methods and various chromatographic techniques. Capillary electrophoresis (CE), a relatively new separation technique with very high resolution power, and Particle Induced X-Ray Emission (PIXE) were used for the analysis of ball point pen inks. In comparison to water soluble fountain pen inks, ball point inks are less soluble or insoluble in water and these inks contain only few components. The study focused on the optimization of the separation of ink extracts from paper material of commercially available inks with respect to resolution and analysis time. During the method development process different buffers, organic modifiers, and surfactants were tested. Good results were obtained with a 50 mM borate buffer pH 9.0 containing 50% acetonitrile. Reproducible extraction procedures as well as separations enables one to perform the quantification of the ink peaks within 1–8% standard deviation for parallel extractions of the same ink. Electropherograms of 20 inks of various origin showed patterns which were in most cases distinctly different from each other. PIXE measurements with an external proton beam were used to determine the metal composition. The ratio of the peak areas for copper and zinc as well as differences in the elemental composition could be used to distinguished between the samples. No coincidence was observed between samples hardly distinguishable by electrophoretic separations and by PIXE-measurements. Samples with nearly identical metal composition showed different peak pattern in the electropherograms, and nearly identical electrophoretic behavior of two or more samples was accompanied by quite different copper/zinc-ratios or supplementary metals identified by PIXE.

Fourteenth-century documents of the Knights of St. John of Jerusalem: analysis of inks, parchment and seals

Summary The national Library of Malta in Valetta comprises a unique collection of the documents of the Order of St. John of Jerusalem (the Knights of Malta). In 1988 the first conservation survey was initiated and funded by the Fulbright Council of International Exchange of Scholars followed by a conservation pilot project supported by the Samuel Kress Foundation in 1989. Selected volumes documenting the earliest history of the Knights were examined from a conservation and analytical point of view. The conservation needs of the collection were addressed in a 1992 publication. The focus of this paper is analysis of the grounds, inks and seals from volume 21 which dates between 1336 and 1373. All the documents were written on parchment in iron-gall ink. Four documents retained their original seals, one of lead and three of wax. Analysis was carried out using x-ray diffraction, scanning electron microscopy with energy dispersive analysis, and Fourier transform infrared analysis, at the Smithsonian Center for...

Separation and Comparison of Fountain Pen Inks by Capillary Zone Electrophoresis

Abstract The analysis of inks as part of the detection of fraudulent documents is a small but important part in the operation of a forensic laboratory. Apart from optical methods, multiple thin layer chromatography (TLC) is used to separate, compare and distinguish inks based on their dye composition. Capillary electrophoresis (CE), a relatively young separation technique with very high resolution power, was used for the analysis of water soluble fountain pen inks. Inks are complex mixtures of synthetic organic and inorganic dyes, surfactants, resins and other components. The study focused on the optimization of the separation of 10% aqueous solutions of commercially available inks with respect to resolution and analysis time. During the method development process different buffers, organic modifiers and surfactants were tested. Good results were obtained with a 100 mM borate buffer at pH 8.0 containing 20% methanol. The separations were reproducible and led to baseline resolution of almost all components of blue and black fountain pen inks. Electropherograms of 15 inks of various manufacturers and countries of origin showed patterns which were in the most cases distinctly different from each other. Initial studies of the separation of extracts of inks from paper were successful and are reported here as well. Therefore, it was concluded that CE is a powerful tool for the identification of water soluble writing inks.

Separation, comparison and identification of fountain pen inks by capillary electrophoresis with UV-visible and fluorescence detection and by proton-induced X-ray emission

The analysis of inks as a part of the detection of fraudulent documents is a small but important aspect of forensic science. The present study was focused on the separation of components of commercially available original fountain pen inks and on different paper substrates by capillary electrophoresis and proton-induced X-ray emission (PIXE). Electropherograms of inks from various manufacturers and countries separated in borate buffers with various methanol contents showed patterns which were in most cases distinctly different from one another. UV-Vis scans and fluorescence detection at different excitation and emission wavelengths have been used to compare similar mixtures and ink extracts from paper with the original ink composition, to identify concurrences or differences in the spectra of main and trace components and to improve the discrimination power of the technique in this way. Extraction conditions, like solvent composition, extraction time, paper carrier material, age of the ink and ink concentration have been examined with respect to signal intensity and the number of detectable components. PIXE spectra of ink samples on different paper substrates have been recorded to determine the elemental composition of the samples and to obtain additional information about the chemical composition of the dyes.

Further results from PIXE analysis of inks in Galileo's notes on motion

We have recently analysed the inks in some of the folios of Vol. 72 of Manoscritti galileiani, kept at the Biblioteca Nazionale Centrale di Firenze, which contains a collection of loose handwritten sheets containing undated notes, data from experiments and propositions on the problems of motion from different periods of Galileo's life. This paper reports specific results obtained from the analysis of some of these propositions, which allowed to make a contribution to their chronological attribution and therefore to the solution of some historical controversies. Even in the case where the “absolute” chronological attributions could not be made on the basis of comparison with dated documents, the PIXE results provided useful information to deny or confirm the hypothesis that different propositions were written in the same or in different periods.

Recent applications to the study of ancient inks with the Florence external-PIXE facility

In the first part of the paper, the specific advantages of external PIXE in the applications to the analysis of ancient inks are discussed together with some problems in the quantitative analysis of the X-ray spectra as far as low-Z elements are concerned, which however come out to be of minor relevance for a discrimination among different inks, which is the main purpose of these investigations. In the second part, a few examples of the results we have recently obtained are illustrated. By detecting the ink composition we have been able to support attributions of several manuscripts, produced in central Italy from the 12th to the 15th century, to the same or different writers and periods. Within this group of manuscripts, a substantial difference was detected between those of the 12th century and all the others, possibly showing a technological evolution in the ink-making procedures. Finally, we report on the latest results of our project for an ink-based chronological reconstruction of undated documents by Galileo. By these results, such a project has now proved to have good chances of casting some light on controversial dating problems of these documents.

Ink analysis from typed script of electronic typewriters by high performance thin layer chromatography

The analysis of ink from the typed script of seven electronic typewriters is carried out by high performance thin layer chromatography. The resultant R f values and in situ visible spectrum of each resolved band of all the chromatograms indicate that the same chemical composition is being used in six typewriter ribbon inks, but that the seventh one is completely different. The method is, however, a destructive one, but extremely sensitive and may be employed in the routine analysis.

Advantages and limitations of external beams in applications to arts & archeology, geology and environmental problems

The physical and technological problems associated with an external beam setup are discussed, together with advantages and limitations in IBA applications. As far as exit windows are concerned, presently the best choice seems to be 8 μm Kapton® foils. They can last for over one week of beam irradiation under standard conditions and give rise anyway to no sudden rupture. Aluminized Mylar® windows can indeed be obtained in thinner foils, but their resistance under beam bombardment is much poorer. Other possible choices for the window material, which are shortly discussed, are nickel and zirconium foils. In a helium atmosphere, Si(Li) detectors with very thin Be windows (8 μm), used for PIXE analysis, have undergone the problem of gas permeation inside the cryostat, but they always recovered to their original condition with a simple pump and bake procedure. Particle detectors we used for external RBS analysis are cheap, standard silicon-junction, which have shown no significant problem of performance deterioration even after weeks of use. The difficulty of a correct current measurement when operating with an external beam is pointed out. Solutions which have been adopted are either external rotating choppers, on which the yield of beam-induced interactions is sampled, or in-vacuum particle detectors monitoring the RBS spectrum of the exit window itself. The possibility of extracting mubeams as small as 10 μm, e.g. for geological applications, or diffused beams of some mm2, e.g. for environmental applications, is also shortly discussed. In the final part of the paper, some examples are given of recent external PIXE-RBS applications to the analysis of paints and inks of ancient manuscripts. Attributions of miniatures to different artists, tentatively suggested by art-historians, have been strengthened by the IBA measurements. These have shown in some cases that the sources of supply of the raw material were different even though the kind of pigment was the same. From the RBS spectra, preliminary data concerning ink absorption within parchment or paper — which may affect the quantitative determination of ink composition — have been obtained.

External beam RBS in an unenclosed helium environment

The external beam facility installed at the KN-3000 accelerator in Florence, formerly used for PIXE measurements, has been exploited also for RBS analysis. A particle detector has been placed at 135° in a setup structure which also includes the two Si(Li) detectors simultaneously used for PIXE. A helium flow is kept in front of the particle detector and of the one used for low-energy X rays, as well as in the region between the beam exit window and the target; no chamber is used for gas containment, in order to allow us the most complete freedom for target size and for its handling. Gas leaks upwards are limited by a soft rubber lid which is kept in contact with the target itself. Helium saturation of the volume in front of the target and of the detectors is attained with a gas flow of less than 1 ℓ atmmin. All the “user-friendly” features of the existing PIXE facility have been maintained: in particular, video-monitoring the sample with a remotely controlled camera, checking beam position with laser aiming and sampling beam current with a rotating chopper are still possible and easy to perform. Particular care has been taken of particle-detector mounting and detection geometry in order to obtain the best possible energy resolution. The present setup gives an overall system resolution of about 28 keV FWHM, when bombarding ultra thin targets with 1.5 to 3 MeV protons. Further improvements are in progress. Preliminary applications have been performed on samples which may not be placed under vacuum; in particular, combined PIXE-RBS measurements have been done to clarify some problems connected with ancient inks analysis (thickness determination, penetration within the underlying paper or parchment), and to check composition of thin standards evaporated onto polymeric supports.

HPLC Analysis of Printing Inks

Abstract The high pressure liquid chromatography (HPLC) method for analyzing printing inks extracted from documents is described. The procedure is sufficiently sensitive for analysis of small areas of printing inks. The analysis can distinguish between different production lots from the same manufacturer. The method was applied on two forensic cases involving forged documents.

The external PIXE setup for the analysis of manuscripts at the Florence University

The external beam PIXE setup of the 3 MV Van de Graaff accelerator in Florence is extensively used for the analysis of parchments, rulings, inks and miniature temperas of Medieval and Renaissance manuscripts. The beam is collimated to about 200 μm and exits from the vacuum environment through a 8 μm Kapton window. Beam currents from 200 to 500 pA are used; they have been found to produce no visible damage to the examined materials. Two Si(Li) detectors are simultaneously used with different geometries in order to cover the widest possible Z-range of the detected elements: even Na is detected with good sensitivity. A robust and versatile support has been constructed for safe and easy handling of the manuscripts. A laser alignment system allows accurate aiming at the detail of interest. A rotating chopper samples the beam at a frequency of the order of 1 Hz; X-rays produced on a Ni layer evaporated on the graphite vane of the chopper are used for charge normalization, since the weak current pulses would be unreliably measured in air due, in particular, to space-charge effects. An application is shortly presented, concerning the materials used for the “colour” rulings which are found, starting from the 11th century, to delimit the writing field for the copyist.

Application of the Microdroplet Method of X-Ray Analysis to the Characterization of Inks

Abstract This study was undertaken to investigate the application of the microdroplet method of x-ray analysis to the characterization of inks. A methodology to allow the microdroplet method to be applied to ink analysis was designed. Ethylene glycol was the preferred solvent for droplet formation. Pyridine was added to this solvent to improve ink extraction capabilities, and could then be removed selectively by vacuum evaporation. Microdroplets were delivered to a thin film support through the use of a nebuliser. Thin films of celloidin were supported on copper specimen grids which were in turn held on a specially designed carbon holder. A number of different inks were examined using both a previously described method and the newly designed microdroplet technique. Examination of 17 inks from ballpoint pens commonly available in Australia showed that no detectable elements were present that could be used for characterization. This result was in contrast to earlier work by Harada in Japan. Four fountain pen inks were also examined and it was found that all of these inks contained detectable elements that could be used for characterization.