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.     

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.     

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.     

红外差谱技术用于微量混合油漆的比对检验

对交通事故中的漆片检材进行同一物质比对时,某些情况下难以提取到单一的油漆碎片而是两辆车的油漆混合在一起,给物证比对带来困难。红外差谱技术具有辨别混合物中不同成分的功能,因此可应用于交通事故中混合油漆检材的比对检验。本文对一起交通事故的漆片检材,分别用三种方式提取、制样,用红外光谱仪进行分析,借助红外差谱技术对谱图进行处理,排除混合油漆的干扰。处理后得到的谱图与样本的谱图进行比对,结果显示两者主要官能团吸收峰位置、峰型、峰强度基本一致,可出具比对一致的结论。针对混合油漆检材的比对检验,红外差谱技术可提供支持。     

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.     

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.     

Identification of organic pigments in automotive coatings using laser desorption mass spectrometry

When one looks at an automotive coating, one sees color due to pigments. Modern organic pigments, with high molar absorptivities, may be only minor components of the mixture. Laser desorption mass spectrometry (LDMS) has been shown to be a useful tool for the analysis of colorants such as pen ink dyes. Here, LDMS is used to determine its utility for the identification of pigments, in simple media and in more complex paints. Small paint chips can be introduced into the LDMS instrument, and when an ultraviolet laser is focused on a portion of a chip, ions representative of the pigment(s) are selectively formed. Some pigments such as quinacridones and copper phthalocyanine are very stable and are desorbed and ionized intact. In contrast, benzimidazolones, which contain some single-skeletal bonds, form fragment ions. This method proves to be sensitive and convenient, as no sample preparation is required. The presence of inorganic pigments in addition to modern organic pigments can be determined, and pigments can be directly identified in actual automotive paint chip samples.     

Multi-technique comparison of source and primary transfer soil samples: an experimental investigation.

The comparison of soil samples is of long-standing and increasing interest in forensic science. Routine comparisons should involve the use of several techniques in combination. A wide range of analytical techniques can be used, choice being dependent on several factors including sample size and character, time constraints and cost limitations. In this paper results are presented for experiments carried out to test the effectiveness of four of the available analytical techniques (spectro-photometric colour determination, laser diffraction particle size analysis, stable isotope analysis and chemical element analysis) used to compare single source and primary transfer soil samples. Four soil types and five footwear types were used. All four techniques showed excellent precision and good resolving power between soil types. Only relatively small differences were obtained between source and transferred soil samples in terms of colour, stable carbon and nitrogen isotope ratios and elemental chemistry. Slight but significant differences were found in grain size, indicating that the primary transfer process is to some extent grain size selective.     

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。     

Analysis of some commonly found inhalants using gas chromatography-mass spectrometry (GC MS) – Effect of substrates on the identification of inhalants

Inhalant abuse is a serious and ever-evolving problem for our society. Inhalants are abused more commonly by teenagers and adolescents. Inhalants such as glue, paint thinners, correction fluid, and nail paint remover are easily available in the market which makes them readily abused. Out of various methods of abuse, huffing (placing a piece of cloth soaked with inhalant is placed in the mouth), bagging (placing head in a polythene bag containing inhalant), and ballooning (balloons filled with inhalant are used for inhaling vapors through the mouth) are most common. Inhalant abuse results in multiple target organ dysfunction with neuritis and brain damage due to the dissolution of the myelin sheath. In acute poisoning cases, it might cause death due to asphyxia and sudden sniffing syndrome. In such cases, various articles containing traces of inhalants could be retrieved from the scene of incidence and to detect these traces become an important facet of the investigation. However, it might be difficult due to the rapid evaporation of inhalants and the formation of reaction product species. In the present study, an attempt has been made to study the effect of three substrates (balloon, cloth, polythene) on component profiles of four paint thinners and four nail paint removers. The study suggests that although some components are retained, there is the formation of a large number of reaction product species and these must be taken into consideration before furnishing the opinion. These reaction product species might also be inhalant specific which must be further explored.     

Recovery of Spray Paint Traces from Clothing by Beating

Manual recovery of spray paints from textiles using a microscope, the routine method in many laboratories, is often laborious. Beating the clothing with a plastic rod, the routine method used for recovery of glass traces within the authors’ laboratory, is proposed as an alternative. The efficiency of the method was evaluated by spray tests with fluorescent paint. In these tests, paint particles in the acquired debris samples, as well as those remaining on the textiles, were investigated. The results show that beating is an efficient way to recover and concentrate paint particles. A good efficiency for jeans fabric and rough knitwear is reported. The results appeared to be less satisfactory for smooth woven fabric. Application of the method in casework was effective for graffiti paints as well as for flaked car paint.     

Characterization and differentiation of aluminum powders used in improvised explosive devices – Part 1: Proof of concept of the utility of particle micromorphometry

Aluminum (Al) powders are commonly used in improvised explosive devices as metallic fuels, a component of explosive mixtures. These powders can be obtained readily from industrial‐scale and consumer products, and produced using unsophisticated “kitchen chemistry” techniques. This research demonstrates the potential of automated particle micromorphometry for comparisons between known source and questioned Al powders recovered from IEDs, as well as for insight into the method of Al powder manufacture. Al powder samples were obtained from legitimate manufacturers, and 56 samples were produced “in‐house” from Al‐containing spray paints and ball‐milled Al foils. Transmitted light microscope images of Al powder particles were acquired using an automated stage with automated z‐focus; 17 size and shape parameters were measured for all particles. Approximately 37,000–2,500,000 particles/sample were analyzed using an open‐source statistical package with customized code. Dimensionality reduction was required for processing the large datasets: eight of the 17 measured variables were selected based on inspection of the correlation matrix. Data from four subsamples from each of the 56 samples produced using “in‐house” methods were analyzed using ANOVA to assess the within‐ and between‐sample variation. High within‐sample variation was noted; however, ANOVA and post‐hoc Tukey's honestly significant difference (HSD) tests demonstrated that the between‐sample variation was substantially larger than the within‐sample variation. Each sample could be differentiated from all other samples in the test set. Future experiments will focus on ways to reduce the within‐sample variation, and additional statistical and microanalytical methods to classify sources and confidently constrain the method of Al powder manufacture.     

Using Paint to Investigate Fires: An ATR‐IR Study of the Degradation of Paint Samples Upon Heating

Fire investigation is a challenging area for the forensic investigator. The aim of this work was to use spectral changes to paint samples to estimate the temperatures to which a paint has been heated. Five paint samples (one clay paint, two car paints, one metallic paint, and one matt emulsion) have been fully characterized by a combination of attenuated total reflectance Fourier transform infrared (ATR‐IR), Raman, X‐ray fluorescence spectroscopy and powder X‐ray diffraction. The thermal decomposition of these paints has been investigated by means of ATR‐IR and thermal gravimetric analysis. Clear temperature markers are observed in the ATR‐IR spectra namely: loss of ν(C = O) band, >300°C; appearance of water bands on cooling, >500°C; alterations to ν(Si–O) bands due to dehydration of silicate clays, >700°C; diminution of ν(CO₃) and δ(CO₃) modes of CaCO₃, >950°C. We suggest the possible use of portable ATR‐IR for nondestructive, in situ analysis of paints.     

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。     

常见油漆稀料的GC／MS的检验及分类研究

目的对常用油漆稀料的检验分析方法及分类进行研究,并建立SPME-GC／MS对纵火案件中油漆稀料快速、灵敏、准确的分析方法。方法采用SPME-GC／MS法对5种不同型号品牌的常见油漆稀料进行分析。结果确定了样品处理方法和仪器分析最佳条件。实验的5种油漆稀料样本根据组分特征和结构特征的不同可归纳为4类。结论该研究结果可为纵火案件中油漆稀料残留物提供一种新的检验方法和检验依据。     

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.     

Identification and comparison of electrical tapes using instrumental and statistical techniques: I. Microscopic surface texture and elemental composition

Comparisons of polyvinyl chloride electrical tape typically rely upon evaluating class characteristics such as physical dimensions, surface texture, and chemical composition. Given the various techniques that are available for this purpose, a comprehensive study has been undertaken to establish an optimal analytical scheme for electrical tape comparisons. Of equal importance is the development of a quantitative means for sample discrimination. In this study, 67 rolls of black electrical tape representing 34 different nominal brands were analyzed via scanning electron microscopy and energy dispersive spectroscopy. Differences in surface roughness, calendering marks, and filler particle size were readily apparent, including between some rolls of the same nominal brand. The relative amounts of magnesium, aluminum, silicon, sulfur, lead, chlorine, antimony, calcium, titanium, and zinc varied greatly between brands and, in some cases, could be linked to the year of manufacture. For the first time, quantitative differentiation of electrical tapes was achieved through multivariate statistical techniques, with 36 classes identified within the sample population. A single-blind study was also completed where questioned tape samples were correctly associated with known exemplars. Finally, two case studies are presented where tape recovered from an improvised explosive device is compared with tape recovered from a suspect.     

Particle size analysis of soils under simulated scene of crime conditions: the interest of multivariate analyses

Two simulated scenes of crime have been studied. Soil traces adhering to boots, sport shoes and tissues have been compared with control samples using particle size analysis. Comparisons of percentage of particles per class interval and multivariate analyses were used to determine how the size distribution of each suspect sample varied compared to the original distribution. A loss of coarse fractions characterized most of the suspect samples even though they were derived from soils having different distributional patterns. However, the differences between control and suspect samples were found to be more important for soils dominated by extreme size classes than for soils rich in medium size particles. The differences among soil samples from the same source were found to be restricted to the extreme size classes. The finding of significant differences within size classes ranging from 1 to 0.063 mm should be then considered as a dissimilarity sign between trace sample and hypothetic control soil.     

Particle size analysis of soils under simulated scene of crime conditions: the interest of multivariate analyses

Two simulated scenes of crime have been studied. Soil traces adhering to boots, sport shoes and tissues have been compared with control samples using particle size analysis. Comparisons of percentage of particles per class interval and multivariate analyses were used to determine how the size distribution of each suspect sample varied compared to the original distribution. A loss of coarse fractions characterized most of the suspect samples even though they were derived from soils having different distributional patterns. However, the differences between control and suspect samples were found to be more important for soils dominated by extreme size classes than for soils rich in medium size particles. The differences among soil samples from the same source were found to be restricted to the extreme size classes. The finding of significant differences within size classes ranging from 1 to 0.063 mm should be then considered as a dissimilarity sign between trace sample and hypothetic control soil.     

The random presence of glass and paint on the clothing and footwear of members of the general population: A US baseline survey at various seasons

This study assists the interpretation of glass and paint evidence by filling an existing gap in the background occurrence that reflects the socioeconomic and demographic circumstances in the United States. The collection was performed in a college US city (Morgantown, West Virginia) to determine the effect of the type of clothing worn at different seasons on the presence of glass and paint. Tape lifts and sole scrapings (1038) were collected from 210 participants and up to six clothing and footwear areas per individual. Glass fragments were analyzed via polarized light microscopy (PLM), refractive index (RI), micro-X-Ray fluorescence (μXRF), and scanning electron microscopy-energy dispersive spectroscopy (SEM-EDS), while paint specimens were examined by light microscopy and infrared spectroscopy (μFTIR). Higher occurrences of glass and paint were found in the winter season. The winter collection yielded 10 glass fragments and 68 paint particles, whereas the summer collection resulted in one glass fragment and 23 paint particles. The percentage of individuals with traces varied between seasons; 7% of individuals in the winter and 0.9% in the summer had glass, whereas 36% of individuals in the winter and 19% in the summer bore paint. Lastly, when considering the overall garment and footwear areas, glass was detected in 1.4% of the winter set, compared to 0.2% in the summer collection; paint was found in 9.2% of the winter collection, whereas only 4.2% was found in the summer set. There were no instances where both glass and paint were detected on the clothing and footwear of the same individual.