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.     

汽车罩光漆的ATR-FTIR法检验

目的通过对油漆样品罩光漆成膜物质的检验以区分不同汽车厂家的油漆样品。方法采用衰减全反射红外光谱法（Fourier Transform Infrared Spectroscopy Attenuated Total Reflection Spectroscopy,ATR-FTIR）研究15个汽车厂家提供的356份油漆样品的罩光漆成膜物质。结果在所有油漆样品中,丙烯酸漆出现的频率最高,氨基漆出现的频率最低;在所有厂家中,使用丙烯酸漆的厂家最多,使用氨基氨酯混合漆的厂家最少;在使用相同罩光漆的不同厂家的油漆样品中,通过比较红外谱图可以对样品进一步区分。结论 ATR-FTIR法能够在一定程度上区分不同汽车厂家的油漆样品,从而大大缩小侦查范围,对于涉车案件的快速侦破具有非常重要的作用。     

Color analysis of apparently achromatic automotive paints by visible microspectrophotometry

Chromatic secondary pigments are utilized in achromatic automotive paints to create unique paint systems. These pigments may not be observable in reflected light; however, utilizing visible microspectrophotometry (MSP) discriminating data may be gathered. This study analyzed 160 apparently achromatic automotive paints via this technique for spectral evidence of secondary pigmentation. These results were compared with visual observations made via polarizing light microscopy. Positive spectral results were attained in approximately 25% of the black and gray/silver topcoat sample sets, whereas the white topcoat and gray undercoat set yielded no probative spectral data. The black sample set did yield several samples that produced spectral evidence of pigmentation when no visual chromatic data was observed. The results of this study suggest that paint analysis schemes should incorporate visible MSP for apparently achromatic black and gray/silver paint samples.     

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.     

A Two‐Level Model for Evidence Evaluation in the Presence of Zeros*

Abstract: Likelihood ratios (LRs) provide a natural way of computing the value of evidence under competing propositions. We propose LR models for classification and comparison that extend the ideas of Aitken, Zadora, and Lucy and Aitken and Lucy to include consideration of zeros. Instead of substituting zeros by a small value, we view the presence of zeros as informative and model it using Bernoulli distributions. The proposed models are used for evaluation of forensic glass (comparison and classification problem) and paint data (comparison problem). Two hundred and sixty‐four glass samples were analyzed by scanning electron microscopy, coupled with an energy dispersive X‐ray spectrometer method and 36 acrylic topcoat paint samples by pyrolysis gas chromatography hyphened with mass spectrometer method. The proposed LR model gave very satisfactory results for the glass comparison problem and for most of the classification tasks for glass. Results of comparison of paints were also highly satisfactory, with only 3.0% false positive answers and 2.8% false negative answers.     

Characterization of Blue Pigments Used in Automotive Paints by Raman Spectroscopy

Micro‐Raman spectroscopy was applied to forensic identification of pigments in paint chips and provided differentiation between paint samples. Sixty‐six blue automotive paint samples, 26 solid and 40 metallic were examined. It was found that the majority of the collected Raman spectra provided information about the pigments present. However, in some cases, fluorescence precluded pigment identification. Using laser excitation at longer wavelengths or pretreatment to effect photobleaching often resulted in reduced fluorescence, particularly for solid color samples, and allowed pigment identification. The examined samples were compared pairwise taking into account number, location, and intensity of absorption bands in their infrared spectra. The estimated discrimination power ranged from 97% for solid paint samples to 99% for metallic paint samples.     

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.     

裂解气相色谱-质谱法和红外光谱法对红色汽车油漆的比较分析

目的应用裂解气相色谱-质谱法（Py-GC/MS）和红外光谱法（IR）鉴别3种红色汽车油漆,通过二者的比较,考察Py-GC/MS法在微量物证油漆鉴定中的适用性。方法取适量固体样品直接检测。IR检测条件：红外显微镜,透射模式,光阑尺寸100μm×100μm,检测范围为4000-675cm-1。Py-GC/MS检测条件：裂解温度：550℃,裂解时间：0.20min。HP-5MS色谱柱,分流比80∶1;升温程序：起始温度为40℃,保持1 min,然后以8℃/min升至300℃,保持1 min。质谱采用EI源,扫描范围：29~350 amu。结果 3种红色汽车油漆的红外光谱、裂解图谱均能相互区分。通过裂解产物,能获得更多油漆主要成膜物质的成分信息。结论在样品量许可的条件下,应在红外光谱的检测基础上,进一步使用裂解气相色谱-质谱方法来对汽车油漆进行检测,通过互相验证,获得更准确、可靠的油漆鉴定结果。     

Identification of tiny and thin smears of automotive paint following a traffic accident

Three complementary methods in the order of stereomicroscopy, micro-FT-IR spectroscopy and solubility tests were used for the purpose of matching known and questioned paint samples in an auto accident case. Grayish green paint smears scattered on a silvery gray coated plastic bar were taken from a blue car and referred to as questioned samples. Green paint chips were collected as known samples from a green car. These were analyzed to determine whether the paint smears found in the blue car could have been the transfers from the green car. Although each of the three methods, when used alone, suffered from unequal bases for making comparison (i.e., layering whole paint vs. smeared paint), insufficient specificity of methodology and the interfering background coating beneath the smeared paint, the limitations were significantly relieved when three methods were used in combination. Based on the results presented in this report, the questioned grayish green paint smears collected from the blue car and the known green paint chips from the green car are of the same class of paint; that is, the possibility of the above stated paint transfers cannot be eliminated.     

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.     

Survey of crowbar and household paints in burglary cases-population studies, transfer and interpretation

Experimental data useful for the interpretation of paint evidence recovered during burglary cases were obtained. A population study was carried out on 41 blue crowbars seized on suspects in Switzerland and 37 blue paints traces found at burglary scenes. Paint traces were also searched on the blades of 207 crowbars seized by the police in Switzerland and 24 white traces were analysed: these paints were analysed using infrared spectroscopy (FTIR) in order to estimate relative frequencies of each paint type. Simulated contacts were carried out between crowbars and painted wood in order to study the phenomenon of transfer and to evaluate the amount of paint transferred: a total of 198 simulations were carried out including individual, successive and cross transfer. The paint properties such as the chemical composition and its age influenced the amount of paint transferred. Cross transfer from the tool paint to the wood and vice versa was regularly observed. Moreover, secondary transfer of paint coming from the preceding wooden surfaces was also systematically observed: this could establish links between several burglary scenes and a suspected tool. A scenario of a burglary case involving the cross transfer between tool and household paints is proposed as a numerical example: the evaluation of such case was formalised using likelihood ratios based on the experimental data obtained.     

Trace Elemental Analysis of Titanium Dioxide Pigments and Automotive White Paint Fragments for Forensic Examination Using High‐Energy Synchrotron Radiation X‐Ray Fluorescence Spectrometry*

Abstract: High‐energy synchrotron radiation x‐ray fluorescence spectrometry (SR‐XRF) utilizing 116 keV x‐rays was used to characterize titanium dioxide pigments (rutile) and automotive white paint fragments for forensic examination. The technique allowed analysis of K lines of 9 trace elements in 18 titanium dioxide pigments (rutile), and 10 trace elements in finish coat layers of seven automotive white paint fragments. High‐field strength elements (HFSE) were found to strongly reflect the origin of the titanium dioxide (TiO₂) pigments, and could be used as effective parameters for discrimination and classification of the pigments and paint fragments. A pairwise comparison of the finish coat layers of seven automotive white paint fragments was performed. The trace elements in the finish coat layers detected by the high‐energy SR‐XRF were especially effective for identification. By introducing the trace element information of primer and electrocoat layers, all the automotive white paint fragments could be discriminated by this technique.     

Methods for physical stabilization of ashed teeth in incinerated remains

Methods for physically stabilizing the extremely fragile ashed teeth that are often encountered in incinerated human remains were investigated. Results of a questionnaire sent to forensic anthropologists and forensic odontologists disclosed that, for these two groups, the most popular methods currently used are impregnation with a solution of polyvinyl acetate or application of cyanoacrylate cement, respectively. In addition, extracted human teeth were incinerated in the laboratory and impregnated with commercially available preparations of either cyanoacrylate cement, clear acrylic spray paint, hair spray, spray furniture varnish, clear fingernail polish, quick-setting epoxy cement, Duco household cement, polyvinyl acetate polymer in acetone, or self-curing clear dental acrylic resin. Every substance tested successfully stabilized the incinerated teeth. Clear acrylic spray paint was judged the most efficacious overall because of its ease of application, availability, inexpensiveness, and rapidity of setting.     

Locating,Identifying, and Comparing Sub‐visible Paint Particles

Forensic paint comparisons are generally conducted on samples which, while small relative to their source, are still visible to the unaided eye and are thus located and analyzed without great difficulty. Here we demonstrate that a more detailed examination of candidate transfer surfaces can capture materials (questioned samples), even when such traces are invisible to the unaided eye. While certain analytical details (such as layer sequence or a pure FTIR spectrum) may not be obtainable from such traces due to their size and condition, a detailed analysis of the sample characteristics that are analytically accessible may still provide sufficient analytical data to arrive at a probative result. Here we present the application of this approach to a suspected paint transfer case, involving particles of paint as small as 40 μm in size. Using a combination of stereomicroscopy, polarized light microscopy, infrared microspectroscopy, Raman microspectroscopy, and SEM/EDS, all performed on a single, subsample of the original minute particle, it was possible to demonstrate evidence of a two‐way transfer between the suspected sources. Furthermore, the transferred paint particle in one direction could be classified as automotive in nature based on a combination of polymer composition, microscopic texture, and pigment package (which included three specifically identified pigments). This work demonstrates (i) the potential for improving detection limits when searching for a questioned sample, (ii) the potential benefits of higher resolution analyses on samples that would be traditionally labeled as “sample‐size limited,” and (iii) the value of case‐specific interpretation over standardized, one‐size fits all report templates.     

Differentiation of ballpoint pen inks by thermodesorption and gas chromatography-mass spectrometry

Differentiation and classification of ink entries with dated samples of a reference collection are important aspects in the examination of questioned documents. Classification of writing inks is presently achieved by analysis of dyes and colorants contained in the ink. This technique has its limitations in newly developed ink formulations with identical dye composition but differing in their solvents and binder resins. This paper introduces a method for the determination of solvents and binder resins of an ink sample directly from paper without sample preparation. This aim is accomplished by thermodesorption of the sample followed by gas chromatography/mass spectroscopy. The method was tested on numerous samples of ballpoint pen inks, which were subsequently grouped into several solvent and resin subgroups. A case study shows the applicability of the newly developed method.     

A Simple Solubility Tests for the Discrimination of Acrylic and Modacrylic Fibers

In a crime scene investigation, single fibers play an important role as significant trace physical evidence. Acrylic fibers are frequently encountered in forensic analysis. Currently, acrylic and modacrylic are not discriminated clearly in Japan. Only results of FT‐IR, some of acrylics were difficult to separate clearly to acrylic and modacrylic fibers. Solubility test is primitive but convenient useful method, and Japan Industrial Standards (JIS) recommends FT‐IR and solubility test to distinguish acrylic and modacrylic fibers. But recommended JIS dissolving test using 100% N,N‐dimethylformamide (DMF) as a solvent, some acrylics could not be discriminated. In this report, we used DMF and ethanol (90:10, v/v) solvent. The JIS method could not discriminate 6 acrylics in 60 acrylics; hence, DMF and ethanol (90:10, v/v) solvent discriminated 59 of the 60 fibers (43 acrylic and 16 modacrylic fibers) clearly, but only one modacrylic fiber incorrectly identified as acrylic.     

Detection of latent bloodstains beneath painted surfaces using reflected infrared photography

Bloodstain evidence is a highly valued form of physical evidence commonly found at scenes involving violent crimes. However, painting over bloodstains will often conceal this type of evidence. There is limited research in the scientific literature that describes methods of detecting painted-over bloodstains. This project employed a modified digital single-lens reflex camera to investigate the effectiveness of infrared (IR) photography in detecting latent bloodstain evidence beneath a layer or multiple layers of paint. A qualitative evaluation was completed by comparing images taken of a series of samples using both IR and standard (visible light) photography. Further quantitative image analysis was used to verify the findings. Results from this project indicate that bloodstain evidence can be detected beneath up to six layers of paint using reflected IR; however, the results vary depending on the characteristics of the paint. This technique provides crime scene specialists with a new field method to assist in locating, visualizing, and documenting painted-over bloodstain evidence.     

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.     

Ultraviolet illumination as an adjunctive aid in dental inspection

Tooth-colored resin fillings have become increasingly popular as restorative materials. Their presence in the dentition presents a challenge to the clinician and the forensic odontologist, as detection of the fillings can be difficult both visually and radiographically. As they necessarily form part of the unique dentition of an individual, recognition of the resins is important for forensic identification. Alternative light sources have been used with success in various fields of forensic science. In recent years small LED flashlights emitting at specific wavelengths in the ultraviolet light (UV) range have been developed. Their low cost, small size, and ready availability makes their use practical in both forensic dental inspection and clinical settings. UV inspection is of interest because enamel, dentin and dental materials all have differing fluorescent properties when illuminated by UV light. It was one goal of this research to quantitatively assess the fluorescence properties of modern restorative resins in order to predict their behavior during inspection using UV illumination. The second goal was to demonstrate practical use of UV in dental inspection with examples of how different materials fluoresce. Quantitative measurements were obtained for optical emission wavelength and intensity for 15 modern resins using a spectrophotometer. Results indicated that resin brands fluoresce at different wavelengths and with varying intensities. Practical use and comparison of the flashlights revealed that the most useful excitation wavelengths for resin detection were in the UVA range (365 and 380 nm). Porcelain restorations and composite resin fillings exhibited different responses to these two wavelengths and thus use of both is recommended for forensic dental inspection.     

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.