The discrimination of (non-denim) blue cotton

This study was conducted to determine the degree of discrimination obtained between non-denim blue cotton fibres using visible–UV range microspectrophotometry alone. To this end, samples of fibres were taken from 100, non-denim, blue cotton, outer garments, including t-shirts, trousers and jumpers and subjected to analysis by both visible and UV range microspectrophotometry. The results obtained from the samples of each garment were compared to determine if they ‘matched’ or not. From an initial visual comparison of the garments it was possible to subdivide the samples into two populations consisting of 73 ‘dark blue’ garments and 27 ‘mid-blue’ garments. It was found that of the 73 ‘dark blue’ garments, 22 distinct sub-populations could be distinguished using visible range MSP, this figure being increased to 43 when the analysis was extended into the UV range. In the case of the 27 ‘mid-blue’ garments, 9 distinct sub-populations were discriminated using visible range MSP, this figure being increased to 17 when the analysis was extended into the UV range. The discriminating power (i.e. the number of discriminated pairs divided by the number of possible pairs) of visible range microspectrophotometry was calculated as 0.89 for ‘mid-blue’ garments and 0.87 for ‘dark blue’ garments. Extending microspectrophotometry into the UV range increased discrimination by 7%, giving a discriminating power of 0.96 for both mid and dark blue cotton fibres which was similar to that reported by a previous study where this method was combined with light and fluorescence microscopy.Intra-garment variation was found to be negligible. The implications of this study for casework are discussed and a revised analytical pathway for the comparison of this fibre type/colour combination using microspectrophotometry as a primary screening tool, is proposed.     

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.     

Fibres used in the construction of car seats — An assessment of evidential value

The evidential significance of car seat fibres has been investigated. Thirty six samples of car seat fabric were examined and the fibres catalogued according to their morphology and characteristics. The majority of car seat fibres were black or grey thick polyester fibres that were either dyed or pigmented. The MSP spectra produced were unlike those usually obtained from black or grey polyester fibres used in clothing. Tapings taken from car seats were examined for car seat fibres, various types were found showing that these fibres are expected to shed from the fabric albeit in low numbers, unless the vehicle is older. No fibres that matched the samples of the car seat fabric were found on the tapings of the car seats. One hundred garments were examined for car seat fibres, 10% of garments had populations of such fibres present and 41% had at least one car seat fibre present. None of these fibres matched the samples of the car seat fabric or those from the car seat tapings.     

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.     

Enzymatic extraction of dyes for differentiation of red cotton fibres by TLC coupled with VSC

The purpose of this work was to assess the usefulness of thin layer chromatography (TLC) for discriminating single cotton fibres dyed with red reactive dyes. An effective enzymatic extraction procedure with the use of cellulase for the red reactively-dyed cotton fibres was developed and used for the discrimination of fibres derived from 21 garments purchased commercially. Discrimination of the fibres relied on the separation of the extracted dyes by thin layer chromatography (TLC). Four eluents were used to develop the plates with the extracted dyes, and the obtained results were analysed using, among others, video spectral comparator (VSC). Observation of TLC plates in visible, ultraviolet and infrared light allowed unambiguous discrimination of 5 and probable discrimination of 6 of the 21 fibres tested. The remaining fibres were divided into several groups. Comparison of the acquired results with those obtained for the same examination material by standard non-destructive methods used in forensic fibres examinations (transmitted light microscopy, fluorescence microscopy, UV–Vis microspectrophotometry and Raman spectroscopy) has shown that efficiency in fibres differentiation is similar for all methods. TLC coupled with VSC was even found to be more effective in differentiation of red cotton fibres. The chemometric analysis was helpful to discriminate dyed cotton fibres, characterized by very similar colour.     

The use of melting point and refractive index determination to compare colourless polyester fibres

The incidence of polyesters encountered in forensic fibre examinations continues to increase. To meet different consumer needs such fibres can be subjected to many physical and chemical variations during production. Some of these variations are discussed. Accurate comparison of these fibres presents a particular problem to the forensic scientist. Melting point and refractive index determinations were made on various samples of colourless polyesters provided by different manufacturers to assess the comparative value of such information and to find out the possibility of relating it to modifications of the basic polymer. Melting points alone were found to be of little comparative value, but determination of both refractive indices n_∥ and n_⊥ does allow discrimination between samples. Consideration of both melting point and refractive index together may help to provide an insight into polymer variation, though this remains somewhat speculative.     

Classification of narcotics in solid mixtures using principal component analysis and Raman spectroscopy

Eighty-five solid samples consisting of illegal narcotics diluted with several different materials were analyzed by near-infrared (785 nm excitation) Raman spectroscopy. Principal Component Analysis (PCA) was employed to classify the samples according to narcotic type. The best sample discrimination was obtained by using the first derivative of the Raman spectra. Furthermore, restricting the spectral variables for PCA to 2 or 3% of the original spectral data according to the most intense peaks in the Raman spectrum of the pure narcotic resulted in a rapid discrimination method for classifying samples according to narcotic type. This method allows for the easy discrimination between cocaine, heroin, and MDMA mixtures even when the Raman spectra are complex or very similar. This approach of restricting the spectral variables also decreases the computational time by a factor of 30 (compared to the complete spectrum), making the methodology attractive for rapid automatic classification and identification of suspect materials.     

The analysis and comparison of blue wool fibre populations found at random on clothing.

Fifty-eight garments were taped and searched for mid to dark blue wool fibres. These were then removed from the tapings, mounted on slides and examined using a high-power microscope (400x). A total of 2,740 blue wool fibres were identified and visible range microspectrophotometry (MSP) was performed on them. Three hundred independent blue wool populations were identified on 56 of the 58 garments searched. The lack of control fibres meant the spectral range of each population was unknown. The number of populations may have been underestimated by grouping together the fibres that had broad single peaks and a lack of distinguishing features in the spectra. Although blue wool is considered to be a common fibre type, 300 unique spectral shapes were identified by the use of microspectrophotometry alone. This demonstrates that the dyes used in the dyeing of blue wool are variable. Showing that many different populations of blue wool occur on a range of garments should ensure that the forensic scientist does not underestimate or understate the strength of evidence in cases where blue wool is found. Hopefully this work will enlighten scientists and enable them to also assess the true value of their findings when other commonly occurring fibres are encountered.     

The transfer and persistence of automotive carpet fibres on shoe soles

The transfer and persistence of automotive carpet fibres to shoe soles was investigated. It was found that fibres were transferred with the normal activity of a car passenger. Carpet type and shoe sole parameters were significant determinants in the number of fibres that transferred. The average number of fibres was between about one and 33 per sole. Fibres that had been transferred after normal activity only persisted for a few minutes after walking. A survey of the shoe soles of people about to leave their car showed that fibres were usually present. The majority of shoe soles surveyed had less than five fibres with the greatest number of fibres found being 14. The likelihood of finding a large number of fibres on such soles is rare. Fibre composition of automotive carpets showed a high degree of variation. Grey was seen to be a common colour irrespective of the colour of the vehicle body.     

The production of colour coordinates from microgram quantities of textile fibres. Part I

This paper describes a method for defining the colour of small samples of textile fibre in terms of its complementary chromaticity coordinates. The coordinates can be calculated from the absorption spectra of solutions of the dye extracted from fibres and use is made of data taken from published tables. Problems arising from this procedure, its significance for the court going officer, and possible future developments are discussed.     

The variation in the colour of paint on individual vehicles

The Nanospec 10S microspectrophotometer has been used to study the variations in topcoat colour over the external painted surface of a number of vehicles. The colour differences observed between samples of the manufacturers' original finish topcoats from different points on the vehicles were relatively small. Visual inspection of the reflectance spectra obtained from individual paint layers is a satisfactory method for showing that two layers have the same pigment composition.     

Investigating the effect photodegradation has on natural fibres at a microscopic level

It is a known fact that when fabric is left exposed to sunlight photodegradation occurs. However, no study has ever looked at the photodegradation that occurs to individual fibre filaments as commonly recovered from a scene of crime. To look at photodegradation of individual fibres, wool and cotton fabric were dyed using CI Acid Red 27 and CI Direct Red 80 respectively at two depths of shade, 0.25% and 2.0% owf. Pieces of fabric and individual fibre samples were then placed in a Light Fastness Q-Sun 1000 Xenon test chamber which simulated exposure to sunlight over two time periods, 64 h (equivalent to one weeks sun exposure) and 128 hrs (equivalent to two weeks sun exposure). The resulting pieces of fabric and fibres where then examined using high power comparison microscopy, as well as graded for colour fading using SDC Grey Scale for Assessing Change in Colour (including half steps). Results show that in both fibre types, photodegradation occurs in all samples, however, the degree of fading is shown to vary within a given fibre population showing it is unpredictable in nature.     

Basic forensic identification of artificial leather for hit-and-run cases

Single fibers retrieved from a victim's garments and adhered to the suspect's automobile have frequently been used to prove the relationship between victim and suspect's automobile. Identification method for single fiber discrimination has already been conducted. But, a case was encountered requiring discrimination of artificial leather fragments retrieved from the victim's bag and fused fibers from the bumper of the suspect's automobile. In this report, basic studies were conducted on identification of artificial leathers and single fibers from leather materials. Fiber morphology was observed using scanning electron microscopy (SEM), color of these leather sheets was evaluated by microspectrophotometry (MSP), the leather components were measured by infrared micro spectrometry (micro-FT-IR) and the inorganic contents were ascertained by micro-X-ray fluorescence spectrometry (micro-XRF). These two methods contribute to other analytical methods too, in the case of utilized single fiber analytical methods. The combination of these techniques showed high potential of discrimination ability in forensic examinations of these artificial leather samples. In regard with smooth surface artificial leather sheet samples, a total of 182 sheets were obtained, including 177 colored sheets directly from 10 of 24 manufacturers in Japan, and five of them were purchased at retail circulation products. Nine samples of suede-like artificial leather were obtained, 6 of them were supplied from 2 manufacturers and 3 sheets were purchased as retailing product. Single fibers from the smooth surface artificial leather sheets showed characteristic for surface markings, and XRF could effectively discriminate between these sheets. The combination of results of micro-FT-IR, color evaluation by MSP and the contained inorganic elements by XRF enabled to discriminate about 92% of 15,576 pairs comparison. Five smooth surface samples form retailing products were discriminated by their chemical composition into four categories, and in addition color information to this result, they were clearly distinguished. Suede-like artificial leather sheets showed characteristic extra-fine fibers on their surface by the observation of SEM imaging, providing high discriminating ability, in regard with suede-like artificial leather sheets were divided into three categories by micro-FT-IR, and the combination of these results and color evaluation information, it was possible to discriminate all the nine suede-like artificial leather sheets examined.     

The kinetics of colour change in textiles and fibres treated with detergent solutions: Part I—Colour perception and fluorescence microscopy analysis

The aim of this study was to assess colour changes that occur in several types of commonly available textiles as a result of the long-term effects of various popularly used laundry detergents. A 14 day experiment was conducted using blue, red and grey/black cotton, wool, acrylic and polyester textiles. Colour changes were evaluated through the visual comparison of the colour of the textile samples against that of the untreated (control) material.The kinetics of the changes in the colour of the fibres were monitored using fluorescence microscopy (UV excitation filter). The conclusions include an assessment of the observed changes from a fibre analysis expert's point of view, as well as that of an average user/consumer of the products involved.     

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.     

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.     

Examination of lubricating oils by infrared spectroscopy

Approximately 60 oil samples obtained from the chassis of various motor cars have been examined by infrared spectroscopy. The samples were oils from the engine, gearbox and back-axle. Differences in absorbance of some absorption bands in the infrared spectra (IR) of oil samples were observed. An optimal set of absorption bands was chosen, which was used for quantitative comparison of slightly differing spectra. The significance of differences was tested using Hotelling's T²-test.     

The kinetics of colour change in textiles and fibres treated with detergent solutions: Part II — Spectrophotometric measurements

The aim of this study was to assess colour variations that occur in several types of textiles and their constituent fibres, resulting from the long-term influence of various laundry detergents. A 14-day experiment was conducted using blue, red and grey/black cotton, wool, acrylic and polyester textiles. The spectrophotometric measurement of colour changes in fabric samples and test solutions, as well as the microspectrophotometric analysis of colour changes in single fibres were described. An evaluation of the observed colour changes from a forensic fibre analysis expert's point of view, as well as that of an average user/consumer of the textiles and laundry detergents is also provided.     

A study to investigate the evidential value of blue and black ballpoint pen inks in Australia

The aim of this project was to investigate the evidential value of blue and black ballpoint pen inks in Australia. For this purpose, 49 blue and 42 black ballpoint pen inks, of different brands, models and batches, representative of those ballpoint pens available on the Australian market at the time of the study, were analysed by three techniques: filtered light examination (FLE); reflectance visible microspectrophotometry (MSP); and thin-layer chromatography (TLC). The results showed that the power of the individual techniques to discriminate inks between and within brands, models and batches varied, the most informative techniques being TLC>FLE>MSP. The greatest degree of differentiation was achieved when using a combined sequence of techniques, the discriminating power being 0.99 and close to 1 for blue and black inks, respectively (different brands and models). In respect to the discrimination between different batches of a same brand and model, it was shown that 14 out of the 33 pairs compared could be discriminated. Overall, this study confirmed the high value of the examination of inks when applied to ballpoint pens available in Australia, especially when a combined sequence of techniques is applied.     

Identifying reliable ions for the statistical differentiation of structurally similar fentanyl analogs

Definitive identification of fentanyl analogs based on mass spectral comparison is challenging given the high degree of structural and, hence, spectral similarity. To address this, a statistical method was previously developed in which two electron-ionization (EI) mass spectra are compared using the unequal variance t-test. Normalized intensities of corresponding ions are compared, testing the null hypothesis (H₀) that the difference in intensity is equal to zero. If H₀ is accepted at all m/z values, the two spectra are statistically equivalent at the specified confidence level. If H₀ is not accepted at any m/z value, then there is a significant difference in intensity at that m/z value between the two spectra. In this work, the statistical comparison method is applied to distinguish EI spectra of valeryl fentanyl, isovaleryl fentanyl, and pivaloyl fentanyl. Spectra of the three analogs were collected over a 9-month period and at different concentrations. At the 99.9% confidence level, the spectra of corresponding isomers were statistically associated. Spectra of different isomers were statistically distinct, and ions responsible for discrimination were identified in each comparison. To account for inherent instrument variations, discriminating ions for each pairwise comparison were ranked based on the magnitude of the calculated t-statistic (t_calc) value. For a given comparison, ions with higher t_calc values are those with the greatest difference in intensity between the two spectra and, therefore, are considered more reliable for discrimination. Using these methods, objective discrimination among the spectra was achieved and ions considered most reliable for discrimination of these isomers were identified.