Forensic applications of infrared chemical imaging: multi-layered paint chips

This paper examines the potential of infrared chemical (hyperspectral) imaging as a technique for the forensic analysis of automotive paint chips in particular, and multicomponent (e.g., layered) samples in general. Improved sample preparation procedures for the infrared analysis of paint chips are detailed, with the recommendation that where mounting resins are chemically incompatible with the sample, it is better to mount and section the sample in a soft wax from which the sections can be removed and pressed into a KBr disk for transmission analysis. Infrared chemical images of multilayered paint chips have been successfully obtained, with the chief advantage over conventional infrared analysis being that thousands of infrared spectra are collected in a few minutes across the whole sample, at a spatial resolution of around 5 microm. As with conventional infrared spectroscopy, chemical species can be identified from their spectra, but the wealth of information available can be also extracted in a number of different ways that make multicomponent spectral (and hence chemical) comparisons between two samples easy to visualize and understand. In one approach, the infrared chemical images of two paint chips being compared side-by-side can be viewed as a "movie," in which each frame is an intensity map of the two samples at a given wavenumber (frequency) value. In another approach, the spectra (pixels) in the image files are classified into chemically similar groups, resulting in a "cluster" image that makes it possible to simultaneously compare all of the layers in two paint chips. These methods are applicable to other multicomponent samples, and also to other chemical imaging techniques.     

Bicomponent acrylic fibers—their characterization in the forensic science laboratory

The increased incidence of bicomponent acrylic fibers received in this laboratory (approximately 30 samples in a five-year period) led us to investigate methods of recognizing, characterising and comparing fibers of this type. Nine varieties present in our own reference collection were examined by brightfield and polarized light microscopy, cross-sectioning, infrared spectroscopy and scanning electron microscopy. The case work samples were compared with these to see whether they reflected any additional varieties. Nearly 70% of them were Orion types, approximately 20% resembled Monsanto X-24 and only one type (encountered twice) did not correspond exactly to any reference sample. Some bicomponent fibers may be easily overlooked by normal microscopical examination. When recognised, they may be characterised into one of the various types using the methods described.     

Single fiber analysis by internal reflection infrared microspectroscopy.

Attenuated total reflection (ATR) is a convenient mode for single fiber analysis by infrared microspectroscopy, particularly when transmission spectra are difficult to obtain or when surface preferenced sampling is desirable. Textile finishes such as spin finishes, anti-static finishes, and permanent press finishes are revealed by ATR techniques. Bicomponent fibers may be analyzed by a combination of ATR techniques, transmission techniques, and spectral subtraction.     

Thermal shrinkage of small single acrylic fibers — A technique of forensic potential

Single fibers less than 1 mm long of nine types of acrylic fibers were thermally shrunk from 85°C to 285°C by hot stage optical microscopy. A surprisingly wide variety of behavior was observed. The temperature for the onset of shrinkage ranged from 105°C to 190°C; total contraction ranged from 2% to 64%; and some fibers contracted rather steadily, whereas others contracted abruptly. Reproducibility of shrinkage was excellent for most monocomponent fibers but was less reproducible for bicomponent fibers. In general, it was found that the technique may be used to discriminate among fiber types within a single fiber generic class using submicrogram sized samples.     

Characterization of condom lubricant components using Raman spectroscopy and Raman chemical imaging

A condom can be described as a protective sheath used as a contraceptive or to protect against sexually transmitted diseases. However, individuals also use condoms during the commission of sexual assaults to prevent identification through deposited biological material. Raman spectroscopy offers a novel approach to identifying the presence of condom lubricant components. Furthermore, Raman chemical imaging expands on conventional Raman spectroscopy to characterize multiple condom lubricant components simultaneously in a manner that effectively demonstrates heterogeneous sample mixtures both spectrally and spatially. Known reference materials, liquid and solid lubricant components of common condom brands were successfully characterized using Raman dispersive spectroscopy and Raman chemical imaging without extensive sample preparation inherent to other analytical methods. The characterization of these materials demonstrates the potential of this technique to become a routine screening method for condom lubricants. This preliminary investigation provides a basis for future studies to determine the feasibility of Raman spectroscopy and Raman chemical imaging for condom lubricant trace detection in case type samples.     

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.     

Investigation into the merits of infrared imaging in the investigation of tattoos postmortem

Infrared imaging has a history of use in the forensic examination of artwork and documents and is investigated here for its wider use in the detection of tattoos on the human body postmortem. Infrared photographic and reflectographic techniques were tested on 18 living individuals, displaying a total of 30 tattoos. It was observed that neither age, sex, age of the tattoo, nor, most significantly, skin color affected the ability to image the tattoos using infrared imaging techniques. Second, a piglet carcass was tattooed and the impact of the decomposition process on the visibility of the tattoos assessed. Changes were recorded for 17 days and decomposition included partial mummification and skin discoloration. Crucially, the discoloration was recorded as greatly affecting the image quality using conventional photography, but was insignificant to the infrared recording of these tattoos. It was concluded that infrared reflectography was beneficial in the investigation into tattoos postmortem.     

The application of infrared chemical imaging to the detection and enhancement of latent fingerprints: method optimization and further findings

Fourier transform infrared (FTIR) chemical imaging allows the collection of fingerprint images from backgrounds that have traditionally posed problems for conventional fingerprint detection methods. In this work, the suitability of this technique for the imaging of fingerprints on a wider range of difficult surfaces (including polymer banknotes, various types of paper, and aluminum drink cans) has been tested. For each new surface, a systematic methodology was employed to optimize settings such as spectral resolution, number of scans, and pixel aggregation in order to reduce collection time and file-size without compromising spatial resolution and the quality of the final fingerprint image. The imaging of cyanoacrylate-fumed fingerprints on polymer banknotes has been improved, with shorter collection times for larger image areas. One-month-old fingerprints on polymer banknotes have been successfully fumed and imaged. It was also found that FTIR chemical imaging gives high quality images of cyanoacrylate-fumed fingerprints on aluminum drink cans, regardless of the printed background. Although visible and UV light sources do not yield fingerprint images of the same quality on difficult, nonporous backgrounds, in many cases they can be used to locate a fingerprint prior to higher quality imaging by the FTIR technique. Attempts to acquire FTIR images of fingerprints on paper-based porous surfaces that had been treated with established reagents such as ninhydrin were all unsuccessful due to the swamping effect of the cellulose constituents of the paper.     

Characterization of multilayered glitter particles using synchrotron FT-IR microscopy

Multilayered glitter particles were cut with a microtome into thin cross-sections and examined using an FT-IR microscope with a synchrotron infrared source. The high brightness of the synchrotron source enabled high-quality infrared spectra to be quickly obtained from individual layers in the glitter particle cross-section, providing additional chemical information that could increase the glitter particle's value as associative evidence in criminal cases.     

运用光谱成像技术区分同色棉纤维

目的研究同色棉纤维的检验方法。方法运用成像光谱法对红、蓝、黑3个颜色组的棉纤维进行区分。结果红色棉纤维的鉴别率为62．2％，蓝色棉纤维的鉴别率为77．8％，黑色棉纤维的鉴别率为69．6％。结论实验结果表明，光谱成像技术可以区分大部分同色棉纤维。拓宽了纤维检验的方法，解决了同色棉纤维的区分问题，该方法能够用于对微量同色棉纤维的快速鉴别。     

An examination of the sequence of intersecting lines using attenuated total reflectance-Fourier transform infrared spectral imaging

In this study, the potential of attenuated total reflectance-Fourier transform infrared (ATR-FTIR) spectral imaging as a technique to determine the sequence of line crossings was examined. The technique was successful in determining the sequence of heterogeneous line intersections produced using ballpoint pens and laser printers. By imaging at characteristic frequencies, it was possible to form spectral images showing the spatial distribution of the materials. By examining the spectral images from the inks, it was possible to determine whether the ink was above or below the toner. In blind testing, ATR-FTIR spectral imaging results were directly compared to those obtained by eight experienced forensic document examiners using methods regularly employed in casework. ATR-FTIR spectral imaging was shown to achieve a 100% success rate in the blind tests, whereas some incorrect sequence determinations were made by the forensic document examiners when using traditional techniques. The technique was unable to image ink-jet printing, gel pens, roller ball pens, and felt-tip pens, and was also unable to determine the sequence of intersecting ballpoint pen lines.     

Preparing samples for the recording of infrared spectra from synthetic fibers.

An improved technique for recording infrared spectra from minute amounts of synthetic fibers by using KBr micropellets is described. The procedure is the same for all commonly encountered synthetic fiber varieties; hence, no preliminary identification is required.     

Evaluation of Raman spectroscopy for the analysis of colored fibers: a collaborative study

A collaborative study on Raman spectroscopy was carried out by members of the ENFSI (European Network of Forensic Science Institutes) European Fibres Group (EFG) on three dyed fibers: two red acrylics and one red wool. Raman instruments from six different manufacturers were tested as well as nine different laser wavelengths ranging from blue (lambda = 458 nm) to near infrared-NIR (lambda = 1064 nm). This represents the largest comparison study of Raman analytical parameters carried out on identical fiber samples. For the chosen fiber and dye samples, red lasers (lambda = 633 and 685 nm) gave the poorest spectral quality whereas blue (458 nm), green (514 nm) and near infrared lasers (785, 830 and 1064 nm) provided average results. Blue (488 nm) and green lasers (532 nm) globally gave the best quality spectra. Fluorescence problems were often encountered with some of the excitation wavelengths and therefore a flexible Raman instrument equipped with different lasers can be recommended to measure forensic fiber samples. The instrument should also be equipped with a Raman microscope in order to be able to focus on a single fiber. This study shows that Raman spectroscopy usually enables the identification of the main dye present in a colored fiber; however, minor dye components are much more difficult to detect. SERRS (Surface Enhanced Resonance Raman Scattering) techniques give an improvement of the dye's spectral intensity but no spectral improvement was observed for the two red acrylic and red wool fibers tested.     

应用红外化学成像技术显现潜在的指印

目的应用红外化学（光谱）成像技术显现潜在指纹。方法采用这种新技术进行显现潜在指印的初步实验。结果显示了其对复杂图案背景上指印突出的显现能力。该成像技术具有物质形态特征检验和物质成分检验双重分析能力，在法庭科学领域具有重要的应用价值。     

The detection and enhancement of latent fingermarks using infrared chemical imaging

The use of a new technique, Fourier transform infrared (FTIR) chemical imaging, has been demonstrated for the enhancement of latent fingermarks on a number of surfaces. Images of untreated fingermarks on glass backgrounds with excellent ridge detail were acquired using infrared chemical imaging. High quality fingermarks on glass backgrounds were also developed using ethyl cyanoacrylate (super glue) fuming and subsequent infrared chemical imaging. This new method allows the collection of images from backgrounds that traditionally pose problems for current fingermark detection methods. The background may, for example, be highly colored, have a complex pattern, or possess other pattern or image characteristics that make it difficult to separate fingermark ridges using traditional optical or luminescent visualization. One background that has proven to be a challenging surface for the development of latent fingermarks is the Australian polymer banknote. To demonstrate the power and applicability of infrared chemical imaging, fingermarks fumed with ethyl cyanoacrylate were successfully imaged from Australian polymer banknotes.     

A further study to investigate the detection and enhancement of latent fingerprints using visible absorption and luminescence chemical imaging

This study investigated the application of chemical imaging to the detection of latent fingerprints using the Condor macroscopic chemical imaging system (ChemImage Corp., Pittsburgh, USA). Methods were developed and optimised for the visualisation of untreated latent fingerprints and fingerprints processed with DFO, ninhydrin, cyanoacrylate, and cyanoacrylate plus rhodamine 6G stain. The results obtained with chemical imaging were compared to the detection achieved using conventional imaging techniques. The Condor significantly improved the detection of many prints, especially those that might be considered poor quality or borderline prints. Prints on newspaper treated with ninhydrin and DFO, and prints on white and yellow paper treated with ninhydrin, benefited the most from chemical imaging detection. In many cases, fingerprints undetectable using conventional imaging techniques could be visualised with chemical imaging. Ridge detail from untreated prints on yellow paper was also detected using the Condor. When prints of high quality were examined, both detection techniques produced quality results. The results of this project demonstrate that chemical imaging offers advantages over conventional visualisation techniques when examining latent fingerprints, especially those that would be considered difficult, such as weak prints or prints on surfaces that produce highly luminescent backgrounds. Standard testing procedures for the detection and enhancement of fingerprints by chemical imaging are presented and discussed.     

显微光谱成像技术在汽车油漆截面检验中的应用

目的对汽车多层油漆的横截面进行分层和比对研究。方法运用显微光谱成像技术对收集的12个省市623个汽车漆片样本进行分层,并对截面结构相同或相似的油漆样本进行了区分。结果 623个油漆样本均可以分层,分析出漆层为两层及以上的油漆样本数占总数的87.26%;截面结构相同或相似的油漆样本能够多层同时区分。结论该方法具有科学及实用价值,检验结果可靠,可见光谱成像技术完全可运用拓展到微量物证的检验中。     

Infrared Imaging of the Crime Scene: Possibilities and Pitfalls

All objects radiate infrared energy invisible to the human eye, which can be imaged by infrared cameras, visualizing differences in temperature and/or emissivity of objects. Infrared imaging is an emerging technique for forensic investigators. The rapid, nondestructive, and noncontact features of infrared imaging indicate its suitability for many forensic applications, ranging from the estimation of time of death to the detection of blood stains on dark backgrounds. This paper provides an overview of the principles and instrumentation involved in infrared imaging. Difficulties concerning the image interpretation due to different radiation sources and different emissivity values within a scene are addressed. Finally, reported forensic applications are reviewed and supported by practical illustrations. When introduced in forensic casework, infrared imaging can help investigators to detect, to visualize, and to identify useful evidence nondestructively.     

A quantitative differentiation method for acrylic fibers by infrared spectroscopy

Absorbance peak areas of nitrile (2240 cm(-1)), carbonyl (1730 cm(-1)) and CH (1370 cm(-1)) groups were obtained for 48 colorless acrylic fibers by infrared (IR) microspectroscopy. The carbonyl signal, related to the comonomers most commonly used in acrylic fibers, was ratioed against the nitrile and CH bands, pertaining to the backbone of the polymer chains. The ratios A1730/A2240 and A1730/A1370, a relative measure of the comonomer content in the fiber, were used to differentiate the samples. A decrease in the crystallinity of fibers has been noted with increasing comonomer content. Relative standard deviation (R.S.D.) of the ratios were 1 and 3% for repetitive analyses on the same location and along the length of the same single fiber, respectively. When different fibers of the same sample were examined, results were reproducible within 6%. This simple method can greatly enhance the evidential value of colorless acrylic fibers, being able to discriminate them and thus helping the Court to better assess their significance.