Application of true color X-ray vision for electron microscopy in fired bullets and gunshot residue investigation

An X-ray color imaging system was used to study primer particles and fired bullets from different .22 rimfire ammunition. The technique proved to be very useful, allowing a ready, concomitant analysis of the morphology of primer particles and their elemental composition. The investigation of the bottom of fired bullets showed that antimony present in the bullet alloy is not evenly distributed, but organized in plates made up of almost pure antimony. Moreover, particles and other traces adherent to lead bottomed bullets containing elements different from lead, therefore, useful to the understanding of primer composition are readily and easily detected.     

Investigating the effect of changing ammunition on the composition of organic additives in gunshot residue (OGSR)

The measurement of the organic additives in smokeless gunpowder is an attractive approach for the detection of handgun use because it provides compositional information that can help associate residues and unfired gunpowder. We investigate several factors that will be required to advance the characterization of organic gunshot residue (OGSR) as a useful forensic tool, including evaluating residue contamination from previously fired ammunition, particle-to-particle compositional variability, and compositional features resulting from the type of firing primer used. Using ammunition loaded with known smokeless powders containing different stabilizers, a sequence of shots was fired from a .357 magnum revolver, and the muzzle exit residues were collected. Compositional analysis of the residues, both in bulk and as single particles, showed only a trace of the previously fired powder in the first shot and none in subsequent shots. In an additional experiment testing conventional leaded and the new lead-free firing primers, the OGSR composition was found not to depend on the primer type.     

Evaluation of the possibility of differentiation between various types of ammunition by means of GSR examination with SEM-EDX method.

Gunshot residues originating from six types of pistol ammunition were studied. Six persons who normally have no contact with weapons fired three times, each person from a different pistol. Samples of gunshot residues were collected from the shooters' hands using aluminium stubs with black carbon adhesive tabs and subjected to examinations of their morphology and elemental content by means of a scanning electron microscope with an energy dispersive X-ray spectrometer in an automatic manner. In a comparative study of the samples, only primer residues were taken into account. The frequency of occurrence of particles representing a certain chemical class against the total number of detected particles was expressed as a percentage. Mutual relations between the frequencies of occurrence of the residues of particular chemical content were found to be different for most of the studied ammunition types using a non-statistical approach--and by means of non-parametric statistical methods (R-Spearman and tau-Kendall correlation coefficients), it was possible to differentiate one ammunition type from each of the other ammunition types examined. The performed examinations have revealed some differences in the frequencies of occurrence of certain chemical classes of primer residues, observed for various types of ammunition. These differences could constitute a valuable contribution to group identifications of ammunition made on the basis of physical and chemical examinations of gunshot residues.     

Computational Approach to Identify Different Injuries by Firearms

Complications arise in the analysis of gunshot wounds to the maxillofacial region, when neither the projectile nor the gun is found at the crime scene. We simulated 5‐ and 15‐cm firing distances at a human mandible to investigate the external morphology of entrance wounds based on fire range. The ammunition models, .40‐caliber S&W, .380‐caliber, and 9 × 19‐mm Luger, were constructed with free‐form NURBS surfaces. In a dynamic simulation, projectiles were fired against mandibular body 3D model at 5 and 15 cm. All entrance wounds presented oval aspect. Maximum diameter and von Mises stress values were 16.5 mm and 50.8 MPa, both for .40‐caliber S&W fired at 5 cm. The maximum energy loss was 138.4 J for .40 S&W fired at 15 cm. In conclusion, the mandible was most affected by .40‐caliber S&W and morphological differences were observable in holes caused by different incoming projectile calibers fired at different distances.     

Glass-containing gunshot residue particles: a new type of highly characteristic particle?

In 0.22 caliber rimfire ammunition, the primer often contains lead or lead and barium compounds. As residues from these primers do not contain lead, barium, and antimony, they cannot be uniquely classified as gunshot residue (GSR) under ASTM designation E 1588-95. In many types of 0.22 caliber rimfire ammunition, the cartridge contains a primer sensitized with glass. In this paper we describe a previously unreported type of GSR particle consisting of glass fused with other primer components. As there appear to be few potential environmental or occupational sources of particles composed of lead and barium compounds fused to glass, particularly borosilicate glass, these particles may have high evidential value. Scanning electron microscopy with energy dispersive X-ray detection (SEM-EDX) and time-of-flight secondary ion mass spectrometry (TOF-SIMS) were evaluated for the characterization of glass-containing GSR particles. The occurrence of glass-containing GSR particles was established in the residue from various brands of 0.22 caliber ammunition, and several sub-types were identified.     

Application of lead isotope analysis in shooting incident investigations

A study was conducted to examine the potential of the considerable variability of the lead isotope compositions in bullets (projectiles) and primers in shooting incident investigations. Multiple-collector inductively coupled plasma mass spectrometry (MC-ICP/MS) was used to analyze lead isotopic compositions in projectiles, cartridge cases, firearms discharge residues (FDR) in barrels of firearms and in the gunshot entries. .22 caliber plain lead and plated ammunition and 9 mm Luger full metal jacket (FMJ) ammunition were employed in shooting experiments using semiautomatic pistols. Cotton cloth served as the target material and two firing distances were tested; 1 cm (near contact) and 2 m distances. It was observed that various mechanical or chemical means of cleaning do not completely remove lead deposits ("lead memory") from barrels of firearms. Nonetheless, it was shown that analysis of lead isotopic composition may provide valuable evidence in investigating specific scenarios of shooting incidents. For instance in a shoot-out where several firearms and ammunition brands are involved, it may be feasible to point out which ammunition and/or firearm caused a particular gunshot entry if the ammunition brands involved (bullets and primers) differ considerably in their lead isotopic composition.     

SEM/EDS analysis and characterization of gunshot residues from Brazilian lead-free ammunition

The exposition to heavy metal-rich airborne due to fire practicing has forced to the development of heavy metal-free environmental ammunition primers all over the world. Here we characterize the GSR elements present in the Brazilian lead-free ammunition produced by Companhia Brasileira de Cartuchos (CBC) and commercialized by MagTech in the U.S. and Europe under the name CleanRange centerfire cartridges. Both first and second generations of CleanRange in calibers 9 mm Luger, .40 S&W, .380 AUTO and .38 SPL were analyzed and compared to regular Brazilian CBC ammunition by scanning electron microscopy/energy dispersive spectroscopy. Differences in composition and morphology of GSR particles from the two generations of CleanRange were observed. The first generation ammunition (found in Europe) presented spherical particles, being strontium the only unique element detected. The second generation (found in the U.S.) produced irregular particles composed mostly by potassium, aluminum, silicon and calcium. We can conclude that identification of GSR derived from CBC second generation lead-free ammunition in suspects' hands may be impossible without the addition of a distinct metallic taggant in the primer composition by the manufacturer.     

Detection of Gunshot Residue on Dark‐Colored Clothing Prior to Chemical Analysis

Detection of gunshot residue (GSR) is an arduous task for investigators. It is often accomplished with chemical tests, which can reveal elements and ions indicating the presence of GSR, but are likely to cause physical alteration to the pattern. In this study, the Spex Forensics Mini‐CrimeScope MCS 400, along with 16 accompanying wavelength filters, was applied to various GSR patterns and target types. Three dark shirt materials, four ammunition calibers, and eight ammunition manufacturers, along with the primer residue of the different manufacturer ammunitions were tested. Results indicate the alternate light source wavelength of 445 nm to be the optimal setting. In addition, target material plays a large role in the preservation of GSR patterns as particles burn. Furthermore, it can be extrapolated that residue, observed from a full round and firing distance of six inches, is mostly composed of unburnt gunpowder residue, not primer residue.     

A Study of the Presence of Gunshot Residue in Pittsburgh Police Stations using SEM/EDS and LC‐MS/MS

Due to possible secondary transfer of gunshot residue (GSR) onto a suspect in police custody prior to sampling, a baseline must be created for the amount of GSR present. With an increase of “lead free” ammunition, testing for both gunpowder and primer GSR is relevant. Seventy samples were collected using carbon‐coated adhesive stubs from four Pittsburgh Police Stations and vehicles to investigate these locations as sources of secondary GSR contamination. These seventy samples were analyzed for primer GSR using scanning electron microscopy‐energy‐dispersive X‐ray spectrometry. One primer GSR particle was detected; no sample was classified as positive for primer GSR. These same samples were then analyzed for gunpowder GSR using liquid chromatography coupled to tandem mass spectrometry to test for akardite II, ethylcentralite, diphenylamine, N‐nitrosodiphenylamine, 2‐nitrodiphenylamine, and 4‐nitrodiphenylamine. Ethylcentralite was quantifiable in two test samples. These results suggest there is a negligible potential for secondary transfer of primer and gunpowder GSR.     

SEM/EDS法和XRF法在电工胶带检验中的应用

目的探索电工胶带带基的元素检验方法。方法利用扫描电镜/能谱法（SEM/EDS）对电工胶带带基中的主体元素进行定量分析,通过SPSS软件对SEM/EDS定量分析法检测出的主体元素（Cl和Ca）相对含量进行统计分析;利用X射线荧光光谱法（XRF）对电工胶带带基中的微量元素进行定性分析。结果34个品牌红色电工胶带组成的561组样品对通过SEM/EDS定量分析法可以区分539组,区分率达到96.1%;根据XRF法定性分析测出的Mg、Al、Si、S、Ti、Sb、Ba、Pb微量元素的不同组合可将34种电工胶带分成11组,两种方法结合可使不同品牌红色电工胶带的区分率达到98.4%。结论SEM/EDS法和XRF法结合可以实现同种颜色、不同品牌电工胶带的高效区分。     

Detecting Gunshot Residue from Sellier & Bellot Nontox Heavy Metal‐free Primer by in situ Cathodoluminescence

Gunshot residue (GSR) from the discharge of ammunition can provide crucial information in reconstructing criminal cases. Traditional primers create particles of heavy metals such as lead, barium, and antimony. In forensic laboratories, automatic inorganic particle detection is performed by scanning electron microscopy (SEM), using the backscattered electron signal to search for bright residues among the many darker environmental particles, due to higher electron density of the former. Some innovative primers, indicated as heavy metal‐free (HMF), produce a residue of elements with atomic numbers below 21, urgently demanding new detecting solutions. For the first time, residues from Sellier & Bellot Nontox HMF primer are demonstrated to emit visible light under electron beam stimulation in a SEM. Cathodoluminescence is then proposed as a promising tool to both detect and characterize residues in forensic cases involving HMF primers, with minor changes to traditional analytical apparatus used for inorganic GSR analysis.     

Proper assessment of the JFK assassination bullet lead evidence from metallurgical and statistical perspectives

The bullet evidence in the JFK assassination investigation was reexamined from metallurgical and statistical standpoints. The questioned specimens are comprised of soft lead, possibly from full-metal-jacketed Mannlicher-Carcano (MC), 6.5-mm ammunition. During lead refining, contaminant elements are removed to specified levels for a desired alloy or composition. Microsegregation of trace and minor elements during lead casting and processing can account for the experimental variabilities measured in various evidentiary and comparison samples by laboratory analysts. Thus, elevated concentrations of antimony and copper at crystallographic grain boundaries, the widely varying sizes of grains in MC bullet lead, and the 5-60 mg bullet samples analyzed for assassination intelligence effectively resulted in operational sampling error for the analyses. This deficiency was not considered in the original data interpretation and resulted in an invalid conclusion in favor of the single-bullet theory of the assassination. Alternate statistical calculations, based on the historic analytical data, incorporating weighted averaging and propagation of experimental uncertainties also considerably weaken support for the single-bullet theory. In effect, this assessment of the material composition of the lead specimens from the assassination concludes that the extant evidence is consistent with any number between two and five rounds fired in Dealey Plaza during the shooting.     

The Relationship Between the Surface Morphology and Chemical Composition of Gunshot Residue Particles

In this study, chemical composition and morphology of gunshot residue (GSR) of 9 × 19 mm Parabellum‐type MKE (Turkey)‐brand ammunition were analyzed by scanning electron microscope and energy dispersive X‐ray spectrometer. GSR samples were collected by “swab” technique from the shooter's right hand immediately after shooting. According to general principles of thermodynamics, it is likely that the structures will have a more regular (homogeneous) spherical form to minimize their surface area due to very high temperatures and pressures that occur during explosion. Studied samples were collected under the same conditions with the same original ammunition, from the same firearm and a single shooter. This is because many other variables may affect size, structure, and composition in addition to the concentrations of elements of the structure. Results indicated that the chemical compositions are effective in the formation of GSR morphological structures.     

Image analysis of gunshot residue on entry wounds: II – A statistical estimation of firing range

A statistical investigation of the relationship between firing range and the amount and distribution of gunshot residue (GSR), used automated image analysis (IA) to quantify GSR deposit resulting from firings into pig skin, from distances ranging between contact and 45 cm. Overall, for a Ruger .22 semi-automatic rifle using CCI solid point, high velocity ammunition, the total area of GSR deposit on the skin sections decreased in a non-linear fashion with firing range. More specifically there were significant differences in the amount of GSR deposited from shots fired at contact compared with shots fired from distances between 2.5 and 45 cm; and between shots fired from a distance of 20 cm or less, with shots fired at a distance of 30 cm or more. In addition, GSR particles were heavily concentrated in the wound tract only for contact and close range shots at 2.5 cm, while the particle distribution was more uniform between the wound tract and the skin surfaces for shots fired from distances greater than 2.5 cm. Consequently, for future scientific investigations of gunshot fatalities, once standards have been established for the weapon and ammunition type in question, image analysis quantification of GSR deposited in and around the gunshot wound may be capable of providing a reliable, statistical basis for estimating firing range.     

Primer residue analysis of ammunition of Indian origin by neutron activation analysis

The primer residues of ammunition manufactured in India have been analysed by neutron activation analysis (NAA). Since NAA is rather insensitive for lead, attention was confined to the elements antimony, barium, copper and mercury. The element/element combinations detected in significant amounts were (Sb), (Ba, Hg), (Ba, Cu, Sb), (Cu, Hg, Sb) and (Hg, Sb). The present study reveals the presence of Hg from mercury fulminate in priming compositions long discontinued in most ammunition of foreign origin. The presence of Hg can be advantageous in certain situations where the matrix on which the residue is deposited contains high levels of antimony such as clothing made of synthetic fibres. Caution is also required in interpreting the Cu values as being solely due to a jacketed projectile.     

Preparation of a Ytterbium‐tagged Gunshot Residue Standard for Quality Control in the Forensic Analysis of GSR

Preparation of a ytterbium‐tagged gunshot residue (GSR) reference standard for scanning electron microscopy and energy dispersive X‐ray spectroscopic (SEM‐EDS) microanalysis is reported. Two different chemical markers, ytterbium and neodymium, were evaluated by spiking the primers of 38 Special ammunition cartridges (no propellant, no projectile) and discharging them onto 12.7 mm diameter aluminum SEM pin stubs. Following SEM‐EDS microanalysis, the majority of tri‐component particles containing lead, barium, and antimony (PbBaSb) were successfully tagged with the chemical marker. Results demonstrate a primer spiked with 0.75% weight percent of ytterbium nitrate affords PbBaSb particles characteristic of GSR with a ytterbium inclusion efficiency of between 77% and 100%. Reproducibility of the method was verified, and durability of the ytterbium‐tagged tri‐component particles under repeated SEM‐EDS analysis was also tested. The ytterbium‐tagged PbBaSb particles impart synthetic traceability to a GSR reference standard and are suitable for analysis alongside case work samples, as a positive control for quality assurance purposes.     

Analysis of primer residue from lead free ammunition by X-ray microfluorescence

In forensic science, the analysis of gunshot residues was traditionally done by the detection of lead (Pb), antimony (Sb) and barium (Ba) usually found in a primer. However, the recent development of lead-free ammunition represents a new challenge for ballistic specialists. This analysis study gunshot residues from primers and ammunitions in the area surrounding bullet holes, a very important tool to determine the shooting distance. The ammunitions used were 9 mm Luger and .38 spl + p calibers, where lead in the primer was replaced with strontium (Sr) and where the lead bullet was plated with copper (Total Metal Jacket). Gunshot analysis results were obtained using an energy dispersive X-ray microfluorescence spectrometer. The method allows the detection and quantification of strontium residues on the target up to a distance of 45 cm.     

An investigation of two methods of DNA recovery from fired and unfired 9 mm ammunition

Cartridge cases are often recovered from crime scenes involving firearms and, in the United Kingdom (where gun possession is strictly controlled), these are commonly from 9 mm calibre ammunition. The ability to obtain informative DNA profiles from touch DNA on recovered cartridges could have a significant impact on the investigation of that type of offence. However, this avenue may not be routinely considered as investigators in the UK have historically had a low expectation of obtaining useful DNA profiles. This stance may not be unreasonable given that (a) only trace amounts of DNA are likely to have been transferred onto the cartridge cases through handling; and (b) when the cartridge is spent, the potential deterioration of that DNA caused by the act of discharging the weapon.We introduce a novel semi-automatable method using direct lysis for the recovery of DNA from ammunition and compare it with a traditional double-swabbing method (using wet and dry swabs). DNA profiling of the DNA recovered using both methods was carried out using the ESI17 FAST STR system (Promega). This demonstrated a significant increase in DNA recovery using the direct lysis approach, and correspondingly improved STR results.We also investigated the effect on the recovery and profiling of DNA from fired, and unfired, 9 mm cartridges using the direct lysis technique. These results demonstrate that DNA suitable for STR analysis can still be recovered from fired ammunition with only slightly reduced yields compared to unfired ammunition. In these experiments, the handler of the ammunition was most commonly either the sole contributor or the major contributor to the recovered DNA profile.     

Shooting distance estimation for shots fired by a shotgun loaded with buckshot cartridges

The present study was carried out to clarify the problem of shooting distance estimation, by studying shots fired with buckshot ammunition in 12 gauge shotgun.For this purpose, the pattern diameter (PD) and the distances between buckshot (DBB) within the pattern were evaluated.Experimental shots were carried out with three differently choked barrels: full, half and cylinder; Winchester-Western OOB and OB buckshot ammunition were used.The results show that the estimation of shooting distance, based on the present parameters, is scarcely reliable especially when this estimation must be calculated on the basis of only a few wound holes on which measurements are made.     

Experimental evaluation of the impact of seating depth variations on observed marks on primers

Although the examination of bullet and primer striae patterns is still a very important task in forensic ballistics, a fundamental explanation or theoretical model for reasoning about the (ir)reproducibility of the observed marks is still non-existing. More specifically, it is still unclear which ammunition production or firing condition parameters may play an important role in the striae and marks formation process. From a practical point of view this situation is unfortunate because a proper knowledge of these parameters and conditions could help underpin and explain certain differences found in actual casework investigations. Additionally, a proper understanding of these issues could allow examiners to select or develop a near-optimal test firing procedure by using more detailed and controlled variations of certain intra- and/or inter-ammunition parameters than the ones that are in use today. In this paper, we discuss the results of an experiment aimed at evaluating the impact of primer seating depth variations on observed primer striae and other marks. First, three sets of cartridge cases with different seating depth intervals were selected. Second, each of these sets were fired consecutively using a selected pistol. Finally, the cartridge cases were examined using both traditional optical microscopes and three-dimensional (3D) profilometer techniques. The results reported in this paper show that in our experiments no important impact of the initial primer seating depth on the observed primer striae patterns could be found, but that the firing pin impression does seem to change if the initial seating depth is larger than a certain threshold.