Materials Chemistry and Physics 81 (2003) 345348

SEMEDXa useful tool for forensic examinations

G. Zadora , Z. Bro ek-Mucha z
Institute of Forensic Research, 9 Westerplatte St., Cracow 31033, Poland

Abstract There are two main aims of forensic examination of the physical evidences. The rst aim is comparison of the evidence with the reference material (called discrimination). The task is to nd out whether they could have come from the same object. The second aim, when there is no comparative material available, is a classication of the evidence sample into a group of objects taking into account its specic chemical and physical properties. Scanning electron microscopy with energy dispersive X-ray spectrometry (SEMEDX) is a powerful tool for forensic scientists to classify and discriminate evidence material because they can simultaneously examine the morphology and the elemental composition of objects. Moreover, the obtained results could be enhanced using some methods of chemometric analysis. A few examples of problems related to the classication and discrimination of selected types of microtraces are presented. 2003 Elsevier Science B.V. All rights reserved.
Keywords: SEMEDX; Forensic examination; Microtraces; Chemometry

1. Introduction Fragments of various materials such as glass, paints, bres and gunshot residues are frequently present at the scene of such events as car accidents, burglaries, ghts or crimes committed with the use of re arms. Very small fragments of those materials that arise during these events can be recovered from hair, hands, clothing and shoes of participants and witnesses of the events and provided as an evidence at a court. One of the tasks of forensic examinations is identication and classication of objects. For instance, it is necessary to know whether gunshot residues are present in a sample taken from suspects hands or that a glass fragment recovered from suspects clothes could originate from a car window or another group. The second task of forensic examinations is a comparison of traces collected from the scene of crime with the evidence materials (e.g. microtraces recovered from a suspects clothes). The task is to nd out whether they could have came from the same object. In order to solve the above-mentioned problems it is necessary to obtain information on both the morphology and the elemental contents of the analysed objects. An observation of the morphology of the sample is carried out, using various optical microscopes, that enable one to observe objects at the magnications of hundreds of times. In case when the
Corresponding author. Tel.: +48-12-422-87-55; fax: +48-12-422-38-50. E-mail address: gzadora@ies.krakow.pl (G. Zadora).

information on morphology is insufcient, some physical and chemical examinations are to be performed. For these tasks a number of analytical methods can be utilised [13]. Traces such as fragments of glass, paints or gunshot residues most often occur in very small quantities. Thus, sensitive analytical methods are required in order to obtain satisfactory results from small amounts of sample. For the selection of proper analytical methods one should take into account the fact that the method is not allowed to destroy the samples because the material might be re-used. One of these non-destructive methods is scanning electron microscopy with an energy dispersive X-ray spectrometry (SEMEDX). It is a powerful tool for forensic purposes because one can examine objects considering their morphology and the elemental composition. Moreover, the obtained results can be evaluated by using suitable methods of chemometric analysis. The aim of this work is the presentation of an SEMEDX method for application in forensic purposes at the Institute of Forensic Research, Cracow, Poland.

2. Analytical equipment The examination of gunshot residues, glass and car paints were carried out, using a scanning electron microscope JSM-5800, made by JEOL, Japan, with an energy dispersive X-ray spectrometer Link ISIS 300, Oxford Instrument, UK. The samples were covered with carbon, using a sputtering unitSCD 050, BAL-TECH, Switzerland.

0254-0584/03/$ see front matter 2003 Elsevier Science B.V. All rights reserved. doi:10.1016/S0254-0584(03)00018-X

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Fig. 1. Inorganic gunshot residue of 20 m in diameter.

2.1. Gunshot residues Gunshot residues can be of organic and inorganic nature. Organic residues originate from the propellant: unburned and partially burned gun powder particles, some products of their transformation and also particles of lubricants. Inorganic residues, mostly metallic, originate from the primer as well as from metallic parts of cartridge and the weapon itself. Among them only particles originating from the primer reveal specic chemical content and characteristic morphology: regular or distorted spheres of linear dimension of micrometers (Fig. 1). Their morphology is an effect of extreme

conditions taking place during explosions of the primer and propellant initiated by the hit of the ring pin in the primer (high temperature and high pressure, and then fast expansion and cooling), whereas the chemical contents is a derivative of the content of the primer. Most frequently, gunshot residues are collected from the suspects hands, where the concentration of these traces is maximal immediately after shooting. In case more time has elapsed since the event traces should be collected rather from the hair, face and clothes where they usually remain for longer than on hands. Particles detected in the material studied are classied taking into account their elemental content [3]. It has been established from empirical studies that only three-component particles containing lead, antimony and barium are unique primer residues. Accompanying two- and one-component particles called indicative are also characteristic gunshot residues, but particles of a similar elemental contents may be created in other circumstances. Particles containing iron, chromium, nickel, copper, zinc and other elements are typical for the case, projectile and its jacket as well as the barrel. However, they can also originate from subjects of everyday use and thus they cannot be considered as an evidence of rearm shooting. Physicochemical examinations of gunshot residues, called also chemical ballistics, are helpful, e.g. in identication of damages and injuries as the effect of the use of rearms (with indicating the entrance and exit of projectile), estimation of the shooting distance and also establishing, whether a person has used a rearm. Fullling these tasks is very helpful for the reconstruction of an investigated crime. However, new challenges for gunshot residues examiners arise. With a growing frequency the administration of justice asks about the type of ammunition, and so the rearm used in

Fig. 2. Dendrogram as a result of cluster analysis of various types of ammunition: B, Browning 7.65 mm; b, Browning 6.35 mm; L, Luger 9 mm; M, Makarow 9 mm; S, sporting 5.6 mm; T, Tokarev 7.62 mm. Numbers denote individual experiments within the same type of ammunition.

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cases when the only accessible for examinations evidence are gunshot residues. Thus one more task can be formulated, i.e., the identication of an ammunition from the gunshot residues detected. One of the attempts to solve this problem is a systematic study of gunshot residues, originating from various ammunition types and statistical and chemometric evaluation of the analytical data [4,5]. The frequency of occurrence of primer residues, containing a combination of lead, antimony and barium, was taken into account. The performed cluster analysis [6,7] utilising these features showed a promising tendency of grouping am-

munitions according to their types (Fig. 2). This can contribute to at least a group identication of an ammunition in cases, when the only evidence accessible for investigations are gunshot residues collected at the scene of crime. 2.2. Glass The importance of glass as evidence was recognised many years ago. As it was mentioned before, glass as the evidence material often occurs in very small quantities. Thus, investigations of glass samples require sensitive analytical methods providing satisfactory results from small amounts

Fig. 3. A glass classication schemea non-statistical approach: c, car windows; ecb, external glass of car bulbs; eob, external glass of ordinary light bulbs; h, car headlamps; icb, internal glass of car bulbs; iob, internal glass of ordinary light bulbs; o, optic glass; p, container glass; t, tableware; w, window panes.

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of the examined material such us the quantitative elemental analysis using an SEMEDX method. The elemental composition of glass strongly depends on the properties of glass products. Taking into account the difference in the elemental contents of samples collected from various groups of glass objects determined by means of SEMEDX method, a scheme of classication and discrimination of glass was obtained at our institute [79]. Inspection of the obtained results allowed to nd elements, whose ranges of concentration in the considered groups did not overlap. The effect of such a non-statistical approach to the problem of classication of glass samples collected in Poland, is presented in Fig. 3. Only sets 35 were homogenous. The classication of objects in sets 6 and 7 was not possible with the non-statistical approach. The cluster analysis was used to solve the problem of classication in the case of sets 6 and 7. As a result a classication scheme was created that made it possible to classify most of the glass microtraces examined by means of the elemental analysis with SEMEDX method [8]. Moreover, a differentiation of glass objects revealing the same qualitative elemental composition (determined with SEMEDX method) can be achieved using the presented approach based upon a cord distance and Students t-test [9]. 2.3. Car paint The paint coat of a car body consists of a number of successively overlaid paint layers. These layers differ from each other in terms of their ingredients, i.e., resin, pigments and llers. The number of layers making up a car covering depends on its type. In brand new cars and in those that have not been repainted there are only three to four layers. Paint coverings of renovated cars consist of a larger number of layers (sometimes even more than a dozen), including not only enamels, but also putties, painters putties and ground undercoats. In identication and comparative studies of paint chips, scientists dene their macroscopic propertiescolour, shade

and textureand their microscopic properties relating to their morphology (the number and sequence of layers, their thickness and colour). The next stage is a detailed analysis of the chemical content of each layer, including identication of the binder, pigments and llers. SEMEDX can be very useful in the case, when the compared paint samples are similar in the microscopic properties relating to their morphology (the number and sequence of layers, theirs thickness, colour) and the results of infra-red spectroscopy analysis. Thus, the identication of a particular paint layer can be carried out comparing the contents of elements since they are characteristic for a given layer and do not repeat [10]. 3. Conclusions The usefulness of SEMEDX methods in solving problems of analysis of microtraces for forensic purposes was conrmed in the course of international tests, e.g. Forensic Testing Program (Collaborative Testing Services, USA). SEMEDX can be successfully used for forensic purposes since sample preparation is simple and nondestructive. References
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