A further study of dye batch variation in textile and carpet fibres.

Four sets of acrylic fibre samples were obtained from a company that dyes fabrics for the fashion industry. Between seven and ten different batches of fibres constituted each set. Comparison microscopy, visible and UV range microspectrophotometry and thin layer chromatography (TLC) were used to compare the dyes on each batch of fibres within the sets. Only one of the four sets exhibited variation within the batches. The differences were seen when both microscopical and analytical techniques were used. In addition, two further sets of samples had been obtained from a company that produces carpets for the car industry. The first set consisted of 26 batches of acid dyed orange nylon fibres. The second consisted of 21 batches of acid dyed mustard coloured nylon and direct dyed brown viscose fibres blended together. When the first set was viewed under UV light one batch had more pale orange fibres present and they fluoresced more brightly than the other fibres. This could be due to the blending with a different dye batch of fibre or due to poor dye uptake--the latter being more likely. When tested using visible and UV range microspectrophotometry and TLC, further dye batch variation was not detected. The second set was examined after separating the nylon and viscose fibres from each other. The nylon fibres were indistinguishable when a range of microscopical and analytical techniques were employed; however, the viscose fibres showed dye batch variation when TLC was used.     

The importance of thin layer chromatography and UV microspectrophotometry in the analysis of reactive dyes released from wool and cotton fibers

Samples of reactively-dyed wool and cotton were obtained from a range of dye manufacturers, dye distributors and the Forensic Science Service (FSS) Fibre Data Collection. The wool fibers were red in color and had previously been compared using comparison microscopy (CM), visible range microspectrophotometry (VS) and thin layer chromatography (TLC). The cotton fibers were blue and black in color and had not been previously compared. Red, blue and black fibers were chosen because they are often encountered in casework. The usage of reactive dyes to color fibers has increased over the last 10-15 years and these are often seen in casework. Before techniques were available that allowed reactively-dyed fibers to be compared using TLC only CM and microspectrophotometry were routinely carried out. Many laboratories, who had a microspectrophotometer, only had a visible range instrument. It was therefore important to see which techniques provide additional information, that gives greater individuality to fibers, to that obtained from CM. The color was released from the wool and cotton fibres using alkaline hydrolysis and a cellulase enzyme respectively. Many of the red wool samples were differentiated from each other using CM. More differentiation was found using VS and even more when ultraviolet range microspectrophotometry (UV) or TLC was used. Two samples could only be differentiated using TLC because CM, VS and UV failed to separate them. The black cotton samples were predominately differentiated using CM but VS allowed for further differentiation. With the samples used in this project UV and TLC failed to separate the samples further. The blue cotton samples benefited from the use of CM, VS and either UV or TLC to reduce the number of matching pairs. All techniques aided differentiation although with this set TLC and UV proved to be complementary techniques. Results demonstrate that TLC and UV both yield important information over and above that obtained from CM and VS. Although in some parts of the project TLC and UV are complementary if the concentration of the dye in the fiber is not sufficient for TLC or the scientist doesn't wish to 'destroy' the fiber UV would be of more use than TLC.     

The dye classification and discrimination of coloured polypropylene fibres

A sequential extraction and classification scheme for dyed polypropylene fibres is presented together with suitable thin-layer chromatography (TLC) systems for separating the extracted dyes.Pigment coloured polypropylene fibres are unaffected by solvents and are therefore characterised by microspectrophotometry.     

The discrimination potential of ultraviolet-visible spectrophotometry, thin layer chromatography, and Fourier transform infrared spectroscopy for the forensic analysis of black and blue ballpoint inks

The knowledge of the discriminating power of analytical techniques used for the differentiation of writing inks can be useful when interpreting results. Ultraviolet-visible (UV-VIS) spectrophotometry, thin layer chromatography (TLC), and diffuse reflectance Fourier transform infrared spectroscopy (FT-IR) were used to examine a population of 21 black and 12 blue ballpoint writing inks. Based on corroborative results of these methods, the discrimination power for UV-VIS, TLC, and FT-IR was determined to be 100% and 98% for the black and blue inks, respectively. Generally, TLC and UV-VIS can be used to differentiate the colorant components (i.e., dyes and some pigments) found in inks. As FT-IR can be utilized to identify some of the noncolorant components, it was determined to be an excellent complementary technique that can be implemented into an analytical scheme for ink analysis.     

Raman spectroscopy and microspectrophotometry of reactive dyes on cotton fibres: Analysis and detection limits

A collaborative study on Raman spectroscopy and microspectrophotometry (MSP) was carried out by members of the ENFSI (European Network of Forensic Science Institutes) European Fibres Group (EFG) on different dyed cotton fabrics. The detection limits of the two methods were tested on two cotton sets with a dye concentration ranging from 0.5 to 0.005% (w/w). This survey shows that it is possible to detect the presence of dye in fibres with concentrations below that detectable by the traditional methods of light microscopy and microspectrophotometry (MSP). The MSP detection limit for the dyes used in this study was found to be a concentration of 0.5% (w/w). At this concentration, the fibres appear colourless with light microscopy. Raman spectroscopy clearly shows a higher potential to detect concentrations of dyes as low as 0.05% for the yellow dye RY145 and 0.005% for the blue dye RB221. This detection limit was found to depend both on the chemical composition of the dye itself and on the analytical conditions, particularly the laser wavelength. Furthermore, analysis of binary mixtures of dyes showed that while the minor dye was detected at 1.5% (w/w) (30% of the total dye concentration) using microspectrophotometry, it was detected at a level as low as 0.05% (w/w) (10% of the total dye concentration) using Raman spectroscopy. This work also highlights the importance of a flexible Raman instrument equipped with several lasers at different wavelengths for the analysis of dyed fibres. The operator and the set up of the analytical conditions are also of prime importance in order to obtain high quality spectra. Changing the laser wavelength is important to detect different dyes in a mixture.     

Dichroism measurements in forensic fibre examination: Part 3 — Dyed cotton and viscose fibres

A number of dyed cellulosic fibres were examined with plane polarized light on their dichroic behavior by microscopy and microspectrophotometry (MSP-PPL). Significant dichroic effects (mostly hypochromic effects and hypsochromic bands shifts) were reported. The effect is related to the chemical structure: some dye structures always possess dichroism (azo, stilbene, thiazole and oxazine), some dyes demonstrate sometimes dichroic effects (anthraquinoid, indigoid) while other structures never demonstrate dichroic effects (sulphur, diphenylmethanes, triarylmethanes, phthalocyanines). In some cases a different dichroic behavior was found for the same dyes applied on cotton and on viscose.     

Differentiation of blue ballpoint pen inks by positive and negative mode LDI-MS

Usually, the differentiation of inks on questioned documents is carried out by optical methods and thin layer chromatography (TLC). Therefore, spectrometric methods were also proposed in forensic literature for the analysis of dyes. Between these techniques, laser desorption/ionization mass spectrometry (LDI-MS) has demonstrated a great versatility thanks to its sensitivity to blue ballpoint ink dyes and minimal sample destruction. Previous researches concentrated mostly on the LDI-MS positive mode and have shown that this analytical tool offers higher discrimination power than high performance TLC (HPTLC) for the differentiation of blue ballpoint inks. Although LDI-MS negative mode has already been applied in numerous forensic domains like the studies of works of art, automotive paints or rollerball pens, its potential for the discrimination of ballpoint pens was never studied before. The aim of the present paper is therefore to evaluate its potential for the discrimination of blue ballpoint inks. After optimization of the method, ink entries from 33 blue ballpoint pens were analyzed directly on paper in both positive and negative modes by LDI-MS. Several cationic and anionic ink components were identified in inks; therefore, pens were classified and compared according to their formulations. Results show that additional information provided by anionic dyes and pigments significantly increases the discrimination power of positive mode. In fact, it was demonstrated that classifications obtained by the two modes were, to some extent, complementary (i.e., inks with specific cationic dyes not necessarily contained the same anionic components).     

Blocks of colour IV: the evidential value of blue and red cotton fibres.

Samples of blue and red cotton fibres were examined using light and fluorescence microscopy as well as UV/VIS microspectrophotometry and fluorescence microspectroscopy. The degree of fluorescence and spectral variation was recorded. Particular attention was paid to the recurrence of certain spectral patterns. The importance of spectral information in the UV range is emphasized again. Colour plays a critical role in the comparison of cotton fibres in forensic sciences. Normally, fibres producing spectral patterns that are frequently seen will tend to have a lower evidential value in criminal cases as the choice of putative sources is theoretically greater and vice versa. Besides black cotton, blue and red cotton fibres are very frequent in fibre casework. The very high discriminating power using a combination of light microscopy, fluorescence microscopy and UV/VIS microspectrophotometry shows that even blue and red cotton fibres can provide excellent evidence when involved in fibre transfer cases.     

The use of filtered light for the evaluation of writing inks analyzed using thin layer chromatography

Thin layer chromatography (TLC) is a scientific methodology that can be used to compare and characterize ink formulations. Occasionally, when evaluating chromatographic profiles on a TLC plate with ambient light, different ink formulations, or the same inks from different batches, may appear indistinguishable. The use of filtered light can be very effective to illuminate characteristics that are not readily apparent with ambient light. There are a diverse number of components commonly found in writing inks, and it may be that some of them respond to particular wavelengths of energy that are not visible to the unaided eye (i.e., colorless). There has been very little information published that addresses the use of filtered light for evaluating TLC plates. Twenty-nine ballpoint writing ink samples were selected for TLC analysis. Further evaluation using an alternate light source, coupled with the appropriate filter, proved to be an effective means for definitive discrimination in some cases.     

The evidential value of black cotton fibres

Forensic scientists are faced with the problem of estimating the frequency of cotton fibres recovered in casework, in relation to those in the general population. One way of doing this is to consider the degree of spectral variation that occurs within a "block of colour". When a spectral pattern occurs very frequently, the evidential value of the fibres may be so low, that it is not worth considering them as target fibres. Using UV-visible range microspectro-photometry (MSP) spectra were recorded from 88 known black cotton dyes and 225 samples of black cotton taken from various textiles. UV-visible spectra originating from sulphur dyes and from the great majority of reactive and direct dyes can be easily recognised. Vat dyes present a little more difficulty. The degree of spectral variation and consequent discriminating power of MSP varied according to the dye class, from 0.13 for sulphur dyes to 0.93 for reactive dyes. From 99 textiles dyed with reactive dyes, the spectra could be divided into at least 40 varieties showing that these fibres have a high degree of individuality. Within the few direct dyes (11.5%) that were encountered, one basic spectral form predominated, but a number of minor variations were observed. Spectral information below 400 nm (UV-range) is important for making distinctions and is critical in the case of direct dyes.     

Dichroism measurements in forensic fibre examination. Part 4-dyed acrylic and acetate fibres

A number of dyed acrylic and acetate fibre samples were examined with plane polarized light on their dichroic behavior by optical light microscopy (OLM) and microspectrophotometry with plane polarized light (MSP-PPL). It was found that most of these low birefringent fibres possess weak dichroic effects that are very hard to observe with microscopy. However, using MSP-PPL, the linear dichroism could be measured. A comparison between the dichroic effects found for the same disperse dyes on triacetate (TrAc), diacetate (Ac), polyester (PES) and polyamide (PA) shows that the linear dichroism follows the order: PA>PES >TrAc, Ac.     

The use of indigo derivatives to dye denim material.

Recently, attention was again drawn to the use of microspectrophotometry to distinguish between fibres dyed with indigo and seven derivative dyes. Under normal circumstances, fibres dyed with indigo (Vat Blue 1 or CI Number 73000) are not included in fibre-transfer examinations as, being ubiquitous, they do not usually have any evidential value. Indigo substitutes are used for fashion dyeing. If their use is widespread, the assumption that all denim material is dyed with Vat Blue 1 may need revising. A positive finding might make it necessary to reconsider the use of certain denim fabrics as capable of providing target fibres. Fibres from 160 samples of denim articles in current use were examined by microspectrophotometry to determine whether either indigo derivative dyes, or other dyes, had been used instead of the traditional indigo.     

Raman spectroscopy and the forensic analysis of black/grey and blue cotton fibres Part 1: investigation of the effects of varying laser wavelength

Raman spectroscopy was investigated to determine the optimal conditions, mainly laser wavelength/s, for the analysis of the commonly encountered black/grey and blue cotton fibres dyed with reactive dyes. In this first part, a single blue cotton fibre, its three dye components, and an undyed cotton fibre were analysed with five different laser wavelengths from two different Raman microprobe spectrometers. The quality of the spectra, fibre degradation and speed of acquisition were used to determine that, under the conditions used, the 785 and 830 nm lasers gave superior results. The 632.8 nm laser wavelengths provided good results with little acquisition time and no spectral degradation. Results indicate that, at least, the major dye component could be identified using Raman spectroscopy.     

Is it a modacrylic fibre?

This study describes the characteristics of modacrylic fibres and includes over 80 samples (previous and current) representing 15 trade names. Fibre morphology was examined using brightfield microscopy. Signs of elongation were determined using polarised light microscopy. Fibre cross sections were also examined. The generic class of fibre was divided into sub groups using polymer composition as determined by FTIR-microscopy. Microscopically, some modacrylic fibres cannot be distinguished from acrylic fibres. Others display unusual optical and morphological features which are a strong indication of their generic class. The infrared spectra provide information about the co-monomer, termonomers added to produced dye sites, the presence of solvent residue, dyes, and additives, e.g. flame retardant material. The infrared spectra should always be recorded before and after any thin layer chromatographic examination of the dye, otherwise peaks attributable to dyes, which may be a valuable comparative feature in casework will be lost.     

Application of Raman Spectroscopy and Surface‐Enhanced Raman Scattering to the Analysis of Synthetic Dyes Found in Ballpoint Pen Inks*

Abstract: The applicability of Raman spectroscopy and surface‐enhanced Raman scattering (SERS) to the analysis of synthetic dyes commonly found in ballpoint inks was investigated in a comparative study. Spectra of 10 dyes were obtained using a dispersive system (633 nm, 785 nm lasers) and a Fourier transform system (1064 nm laser) under different analytical conditions (e.g., powdered pigments, solutions, thin layer chromatography [TLC] spots). While high fluorescence background and poor spectral quality often characterized the normal Raman spectra of the dyes studied, SERS was found to be generally helpful. Additionally, dye standards and a single ballpoint ink were developed on a TLC plate following a typical ink analysis procedure. SERS spectra were successfully collected directly from the TLC plate, thus demonstrating a possible forensic application for the technique.     

Thin-layer chromatography of dyes extracted from cellulosic fibres

A suitable solvent for the extraction of reactive dyes from cellulosic fibres has been found and thin-layer chromatographic systems for the characterisation of direct, reactive, vat and sulphur dyes extracted from cellulosic fibres have been evaluated. After examining several dyes extracted from manufacturers' pattern cards and casework materials, elution systems for use with the aluminium-backed Merck DC Alufolien Kieselgel 60F₂₅₄ plates have been recommended for direct and reactive dyes. No successful characterisation of the vat or sulphur dyes has been possible.     

The use of linear dichroism in forensic fibre examinations — Part 6. Validation and practical aspects of MSP-PPL

This paper summarizes the results of previous work on the microscopic observation of linear dichroism found in dyed fibres (polyesters, polyamides, wool, silk, cotton, viscose, acrylics and acetates) and in pigmented fibres as well as the measurements on these fibre classes using microspectrophotometry with plane polarized light (MSP-PPL). The validation of this method is discussed and a practical tool is proposed for comparing fibre traces with control fibres. The limitations and strengths of this method are also revised.     

The Discrimination of Colored Acrylic,Cotton, and Wool Textile Fibers Using Micro‐Raman Spectroscopy. Part 1: In situ Detection and Characterization of Dyes

Raman spectroscopy has been applied to characterize fiber dyes and determine the discriminating ability of the method. Black, blue, and red acrylic, cotton, and wool samples were analyzed. Four excitation sources were used to obtain complementary responses in the case of fluorescent samples. Fibers that did not provide informative spectra using a given laser were usually detected using another wavelength. For any colored acrylic, the 633‐nm laser did not provide Raman information. The 514‐nm laser provided the highest discrimination for blue and black cotton, but half of the blue cottons produced noninformative spectra. The 830‐nm laser exhibited the highest discrimination for red cotton. Both visible lasers provided the highest discrimination for black and blue wool, and NIR lasers produced remarkable separation for red and black wool. This study shows that the discriminating ability of Raman spectroscopy depends on the fiber type, color, and the laser wavelength.     

Dichroism measurements in forensic fibre examination. Part 2 — Dyed polyamide, wool and silk fibres

A number of dyed polyamide, wool and silk samples were examined with plane polarized light on their dichroic behavior by optical light microscopy (OLM) and microspectrophotometry with plane polarized light (MSP-PPL). It was found that most of these acid dyed peptidic fibres possess dichroism, but these are weaker than the effects previously described for polyester fibres. The small effects may be not observed, especially for wool, but these can be measured using MSP-PPL.In the three peptidic fibre classes, for the first time, a so called “inverse dichroism” is observed which appears in the absorption spectra as a hyperchromic effect.     

The Analysis of Colored Acrylic,Cotton, and Wool Textile Fibers Using Micro‐Raman Spectroscopy. Part 2: Comparison with the Traditional Methods of Fiber Examination

In the second part of this survey, the ability of micro‐Raman spectroscopy to discriminate 180 fiber samples of blue, black, and red cottons, wools, and acrylics was compared to that gathered with the traditional methods for the examination of textile fibers in a forensic context (including light microscopy methods, UV‐vis microspectrophotometry and thin‐layer chromatography). This study shows that the Raman technique plays a complementary and useful role to obtain further discriminations after the application of light microscopy methods and UV‐vis microspectrophotometry and assure the nondestructive nature of the analytical sequence. These additional discriminations were observed despite the lower discriminating powers of Raman data considered individually, compared to those of light microscopy and UV‐vis MSP. This study also confirms that an instrument equipped with several laser lines is necessary for an efficient use as applied to the examination of textile fibers in a forensic setting.