Application of Infrared and Raman Spectroscopy in Paint Trace Examination

Raman spectroscopy has proved to be a promising technique in forensic examinations, where optical microscopy, micro‐infrared spectroscopy, and microspectrophotometry in the visible and UV range are used for identification and differentiation between paint traces. Often no organic pigments are detected using Fourier transform infrared spectroscopy, because their content in a trace is usually undetectable. Application of a micro‐Raman spectrometer equipped with several excitation lasers helps forensic experts in paint analysis enabling identification of main pigments. Three cases concerning comparative examination of car paint are discussed in detail. The comparison of Raman spectra of paint chips found on clothing of a victim or smears found on body of a damaged car to these of paint chips originated from the suspected car enabled us to identify the car involved in the accident. When no comparative material is available, the method can be useful in establishing the color and make of the car.     

显微红外光谱仪与显微拉曼光谱仪对纺用无色单根纤维的检测

目的研究常见纺用单根无色纤维的有效鉴别方法。方法使用显微红外光谱仪、显微激光拉曼光谱仪研究7大类纺用单根无色纤维的分子光谱。结果显微红外光谱仪、显微激光拉曼光谱仪能有效区分包括棉、粘胶、羊毛、丝、聚酰胺、聚丙烯腈和聚酯在内的7种纤维,是检测单根纤维的有效手段。785nm激发光源是显微激光拉曼光谱仪研究这7类纤维的最佳波长。但由于纺用纤维生产过程的标准化,仅依据红外或者拉曼的峰位置区分同种类、不同产地纤维的效果一般。结论显微红外光谱仪、显微激光拉曼光谱仪是鉴别常见纺用单根无色纤维的有效方法。     

Optical Characterization of Some Modern “Eco‐Friendly” Fibers*

Abstract: Fibers that are termed “eco‐friendly” or “biodegradable” by manufacturers are increasingly being used in textile products such as apparel and carpeting to appeal to the ever more environmentally aware public. As such, these modern fibers are expected to begin showing up more often in forensic casework, and it is important that the forensic examiner recognize them. This study employed polarized light microscopy (PLM) and Fourier transform infrared (FTIR) microspectroscopy to characterize selected fibers of azlon, polylactic acid (PLA), cellulose composites of alginate or chitin, and bamboo (viscose rayon). Fiber cross‐sections, refractive indices, melting points, solubilities, and FTIR measurements were conducted. Results indicate that the azlons and PLA fibers are easily distinguishable from other textile fibers by their optical and chemical properties. The cellulose composites show only small differences in comparison with other cellulose‐based fibers, while bamboo viscose rayon is indistinguishable from normal viscose rayon.     

The effect of ionizing gamma radiation on natural and synthetic fibers and its implications for the forensic examination of fiber evidence

Circumstances of criminal activities involving radioactive materials may mean fiber evidence recovered from a crime scene could have been exposed to materials emitting ionizing radiation. The consequences of radiation exposed fibers on the result of the forensic analysis and interpretation is explored. The effect of exposure to 1-1000 kGy radiation doses in natural and synthetic fibers was noticeable using comparative forensic examination methods, such as optical microscopy, microspectrophotometry, and thin-layer chromatography. Fourier transform infrared spectroscopy analysis showed no signs of radiation-induced chemical changes in any of the fiber structures. The outcome of the comparative methods highlights the risk of "false negatives" associated in comparing colors of recovered fibers that may have been exposed to unknown radiation doses. Consideration of such results supports the requirement to know the context, including the environmental conditions, as much as possible before undertaking a forensic fiber examination.     

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.     

Principal component analysis and analysis of variance on the effects of Entellan New on the Raman spectra of fibers

During the forensic examination of textile fibers, fibers are usually mounted on glass slides for visual inspection and identification under the microscope. One method that has the capability to accurately identify single textile fibers without subsequent demounting is Raman microspectroscopy. The effect of the mountant Entellan New on the Raman spectra of fibers was investigated to determine if it is suitable for fiber analysis. Raman spectra of synthetic fibers mounted in three different ways were collected and subjected to multivariate analysis. Principal component analysis score plots revealed that while spectra from different fiber classes formed distinct groups, fibers of the same class formed a single group regardless of the mounting method. The spectra of bare fibers and those mounted in Entellan New were found to be statistically indistinguishable by analysis of variance calculations. These results demonstrate that fibers mounted in Entellan New may be identified directly by Raman microspectroscopy without further sample preparation.     

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.     

Inter-comparison of unrelated fiber evidence

The foreign textile fibers recovered from one item of evidence from each of 20 unrelated crimes in three categories (bank robbery, kidnapping, and homicide) were cross-compared. The items of evidence were scraped to remove the trace evidence and a sample of the collected fibers was examined using a standard scheme of analysis. The fibers were examined with light microscopy (including polarized light microscopy), fluorescence microscopy, and microspectrophotometry. The fibers were divided into natural and manufactured groups and then categorized by color and generic (polymer) class. Cross-comparing all 2083 fibers resulted in 2,168,403 comparisons, after removing duplicate (same fiber) comparisons. Colorless and denim fibers were excluded from this study. No two fibers were found to exhibit the same microscopic characteristics and analytical properties. Therefore, it is rare to find two unrelated items that have foreign fibers that are analytically indistinguishable. These results corroborate other population studies conducted in Europe and target fiber studies conducted both in the US and in Europe.     

显微红外光谱仪与显微拉曼光谱仪对纺用无色单根纤维的检测

目的研究常见纺用单根无色纤维的有效鉴别方法。方法使用显微红外光谱仪、显微激光拉曼光谱仪研究7大类纺用单根无色纤维的分子光谱。结果显微红外光谱仪、显微激光拉曼光谱仪能有效区分包括棉、粘胶、羊毛、丝、聚酰胺、聚丙烯腈和聚酯在内的7种纤维,是检测单根纤维的有效手段。785nm激发光源是显微激光拉曼光谱仪研究这7类纤维的最佳波长。但由于纺用纤维生产过程的标准化,仅依据红外或者拉曼的峰位置区分同种类、不同产地纤维的效果一般。结论显微红外光谱仪、显微激光拉曼光谱仪是鉴别常见纺用单根无色纤维的有效方法。     

An Examination of the Sequence of Intersecting Lines using Microspectrophotometry

The potential of microspectrophotometry as a technique to determine the sequence of intersecting lines was examined. The technique was used to determine the sequence of heterogeneous line intersections produced using inkpad, stamp‐pad ink and ballpoint pens, gel pens, fountain pens, laser and ink‐jet printers. 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. According to spectral reflectance curves, microspectrophotometry was possible to determine whether the ink was above or below the inkpad/stamp‐pad ink seals. In blind testing, microspectrophotometry technique results were directly compared to those obtained by five experienced forensic document examiners using optical microscopy regularly employed in casework. As the results obtained from the study were positive, microspectrophotometry technique was found to be very successful in determining the sequence of heterogeneous line intersections under some conditions.     

Applications of Blue Light‐curing Acrylic Resin to Forensic Sample Preparation and Microtomy

This study discusses the results of an evaluation of a one‐part blue light‐curing acrylic resin for embedding trace evidence prior to the preparation of thin sections with a microtome. Through a comparison to several epoxy resins, the physical properties relevant to both trace evidence examination and analytical microscopy in general, including as viscosity, clarity, color, hardness, and cure speed, were explored. Finally, thin sections from paint samples embedded in this acrylic resin were evaluated to determine if, through smearing or impregnation, the resin contributed to the infrared spectra. The results of this study show that blue light‐curing acrylic resins provide the desired properties of an embedding medium, generate high‐quality thin sections, and can significantly simplify the preparation of paint chips, fibers and a multitude of other types of microscopic samples in the forensic trace evidence laboratory.     

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.     

High-performance liquid chromatography-ultraviolet-visible spectroscopy-electrospray ionization mass spectrometry method for acrylic and polyester forensic fiber dye analysis

A critical point of comparison between a fiber collected from a crime scene and a fiber from a known source is the color. Fiber dye analysis using thin-layer chromatography or ultraviolet (UV)-visible (Vis) microspectrophotometry provides useful, although limited, data for comparison. High-performance liquid chromatography-electrospray ionization mass spectrometry (LC/MS) overcomes these limitations by integrating chromatography, ultraviolet-visible spectroscopy, and mass spectrometry into a single instrument. In order to evaluate the applicability of the LC/MS to forensic fiber dye analysis, a multi-stage chromatographic method using acidified water and acidified acetonitrile was developed that separated and identified a mixture of 15 basic and 13 disperse dye standards. The LC/MS also detected and analyzed dyes extracted from individual 0.5 cm acrylic and polyester fibers, demonstrating its applicability to this type of analysis. With regard to the analysis of disperse dyes in polyester fibers, the replacement of pyridine with acetonitrile in the extraction system allowed direct injection of the extracts into the LC/MS. The advantage of the LC/MS over other instrumental methods of textile dye analysis is demonstrated by the analysis and differentiation of three black acrylic fibers: two fibers had similar UV-Vis spectra but were differentiated with chromatography and two had similar UV-Vis spectra and chromatograms but were differentiated using the mass spectrometer.     

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 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.     

油性圆珠笔字迹书写时间鉴定的研究综述

本文追述了油性圆珠笔问世以来,字迹书写时间的检验发展过程;总结了静态法,如标准样品比对法和基准物标记法,动态法,如如溶剂萃取法、色谱法、质谱法和光谱法用于鉴定圆珠笔字迹书写时间的研究成果;展望了非破坏性方法在鉴定书写时间上的发展趋势。     

The Evidentiary Significance of Automotive Paint from the Northeast: A Study of Red Paint

This population study was conducted to assess the frequency of physical, microscopical, and chemical properties of automotive paint chips. Population studies of trace evidence provide valuable analytical data for criminalists to assess evidentiary significance. Two‐hundred automotive paint chips were collected from auto body shops from the Northeastern United States. All samples were analyzed using stereomicroscopy, brightfield, and polarized light microscopy. Red paints were targeted for further analysis using a sequence of modern instrumental techniques commonly used by forensic paint examiners: Fourier‐transform infrared (FT‐IR), Raman, and ultraviolet–visible (UV–Vis) microspectroscopy. The discrimination potential of each analytical method was evaluated by inter‐comparing the paint samples. Results demonstrated that macroscopic and microscopic properties were able to differentiate 99.995% of the population (one undifferentiated pair out of 19,900). When combined with either FT‐IR or UV–Vis microspectroscopy, all paints were differentiated. The results of this research lead to the conclusion that one would not expect to encounter two indistinguishable paint chips originating from different sources during the investigation of a single event.     

Raman Spectroscopic Differences between Ephedrine and Pseudoephedrine

Ephedrine (EPH) and pseudoephedrine (PSE) were studied by micro‐Raman spectroscopy and UV resonance Raman spectroscopy excited at 785 and 360 nm, respectively. Raman bands at approximately 245 and 410 cm^?1 for ephedrine have apparent differences from the same bands at approximately 215, 265, 350, 450, and 555 cm^?1 for pseudoephedrine, and these differences can be applied to distinguish between EPH and PSE. Additionally, density functional theory was used for the Raman calculations to obtain results identical to the experimental spectra. This work is expected to expand the applications of Raman spectroscopy in forensic science.     

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.     

On the frequency of occurrence of a peculiar polyester fibre type found in blue denim textiles

In a double murder investigation, the victims were found after a prolonged stay in a drainage canal. In spite of the expectations, fibre examination established a multitude of primary and secondary transferred fibres. One of these fibre types was a colourless polyester fibre possessing a blue coloured molten fibre end. These matched one of the types present in the suspect's blue denim trousers. The aim of this study was to verify the rarity of this peculiar fibre type and more precisely its presence in blue denim textiles. Over five hundred different blue jeans textiles were examined and only one of these presented exactly the same type. The comparison involved microscopy, microspectrophotometry in the visible range and Raman spectroscopy. The results indicate this fibre type is extremely rare in a blue jeans fabrics and that “standard” blue denim should not be disregarded in case work.