Comparing the additive composition of smokeless gunpowder and its handgun-fired residues

Detecting the use of handguns via the determination of the organic additives in smokeless gunpowder residues (OGSR) presents a promising alternative to primer metal residue analysis. Compositional analysis of the gunpowder additives nitroglycerin, diphenylamine, and ethyl centralite provides information that can associate residue samples with unfired gunpowder. We evaluated the composition of seven reloading smokeless gunpowders, both in bulk and as single particles, by ultrasonic solvent extraction/capillary electrophoresis. Handgun-fired residues obtained from three common weapon calibers loaded with the known reloading powders were compared with the unfired powders. In general, the composition of the residues was similar to that found in the unfired powders. For double-base powders, comparing the ratio of the propellant (P) to the total amount of stabilizer (S) for both residue and gunpowder samples proved to be a useful measurement for identification. This P/S ratio demonstrated that the additives in the residues did not greatly change relative to the unfired powder, providing a useful indicator to aid in forensic powder and residue evaluation.     

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.     

Macroscopic observation of the morphological characteristics of the ammunition gunpowder

At the present time, optical examinations are not used in routine to analyze the gunshot residues, except for the counting and the localization of particles. Indeed, the sequence of examinations often starts immediately with destructive techniques, contrary to the widely accepted law saying that we should progress from general to particular and from non-destructive to destructive and which is recommended for all the fields of forensic sciences. When a cartridge is shot, and before the projectile leaves the gun, all the powder grains should must be completely burnt; however, if this ideal case does not happen, it is possible to find unburnt and/or partially burnt gunpowder particles [H.H. Meng, R. Caddy, Gunshot residue analysis-a review, J. Forensic Sci. 42 (1997) 553-570]. The goal of this paper is to study the morphological characteristics of the powder before and after the shot, to establish if it is possible to determine which type of ammunition has been used on the basis of these characteristics. A set of 181 cartridges of different calibers was considered and various tests carried out to evaluate the technique. On the basis of the observation of the gunpowder particles found on the target, a list of potential cartridges can be established with the actually shot cartridge always found among them. It is important to underline that a maximum of eight cartridges were proposed for each experiment. Consequently, the method can be judged very discriminating. A database was then created, including information related to the morphological characteristics of the gunpowder before and after the shot as well as to the class characteristics of the analysed cartridges.     

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.     

Combined Collection and Analysis of Inorganic and Organic Gunshot Residues

Gunshot residue (GSR) analysis and their interpretation provide crucial information on a criminal investigation involving the use of firearms. To date, several approaches have been proposed for the implementation of a combined sampling and analysis of inorganic (IGSR) and organic GSR (OGSR). However, it is not clear at this stage if concurrent analyses of both types of residue might be detrimental to the analysis of IGSR currently applied in forensic laboratories. Thus, this work aims to compare and evaluate three different protocols for the combined collection and analysis of IGSR and OGSR. These methods, respectively, involve the use of a modified stub (with two halves, one for the detection of IGSR and the other for the analysis of OGSR); the sequential recovery of GSR with two stubs mounted with different adhesives (double-sided carbon tape and Tesa® TACK) and the sequential analysis of IGSR and OGSR from a single carbon stub following carbon deposition. The detection of IGSR was carried out using SEM-EDX, while OGSR analysis was performed using ultra-high-performance liquid chromatography–tandem mass spectrometry (UHPLC-MS/MS). Obtained results for experiments performed using Geco Sinoxid^® ammunition indicated that sequential analysis was the most suitable protocol for the combined collection and analysis of both IGSR and OGSR. A higher number of inorganic (characteristic and consistent) particles and higher concentrations of ethylcentralite, N-nitrosodiphenylamine, diphenylamine, and nitroglycerin were recovered with this method.     

Preliminary evaluation of the persistence of organic gunshot residue

The organic components of gunshot residue (OGSR, also called firearms discharge residue (FDR) or cartridge discharge residue (CDR)) have been studied and discussed in the literature. These residues, consisting of particulates such as burned and unburned powder as well as molecular compounds, are rarely used in casework except for purposes such as shooting reconstructions. Molecular compounds that survive the firing event or that are created as a result of the firing event could, with focused research and development, open a new avenue for forensic gunshot residue analysis. In this study, the persistence of organic gunshot residue was evaluated using diphenylamine (DPA) as a target analyte and ion mobility spectrometry (IMS) as the detection system. Samples were collected from hands using a solvent swabbing technique and the swab was analyzed using direct thermal desorption for sample introduction into the IMS. OGSR was found to persist for at least 4h. Although DPA is a widely used industrial compound, analysis of numerous blank and background samples (n～100) did not show any significant response for DPA using this detector. Variations were noted among individuals and as such, the data set does not support estimation of a half-life as has been done for traditional primer residues. No secondary transfers were observed, suggesting the possibility of skin adhesion via interactions between the lipophilic organic compounds and skin lipids. IMS proved valuable as a means of generating patterns for forensic pattern matching and shows promise as a screening tool applied to firearms discharge.     

The identification of two unusual types of homemade ammunition

Illegal homemade ammunition is commonly used by criminals to commit crimes in Taiwan. Two unusual types of homemade ammunition that most closely resembling genuine ammunition are studied here. Their genuine counterparts are studied as the control samples for the purpose of comparison. Unfired ammunition is disassembled, and the morphological, dimensional, and compositional features of the bullet and cartridge case are examined. Statistical tests are employed to distinguish the dimensional differences between homemade and genuine ammunitions. Manufacturing marks on head stamps of the cartridge case are carefully examined. Compositional features of propellant powders, primer mixtures, and gunshot residues are also analyzed. The results reveal that the morphological, dimensional, and compositional features of major parts of the ammunition can be employed to differentiate homemade cartridges from genuine ones. Among these features, tool marks on the head stamps left by the bunter can be used to trace the origin of ammunition.     

Grouping of ammunition types by means of frequencies of occurrence of GSR

An attempt was made to build a classification scheme for gunshot residues (GSR) samples originating from four types of ammunition, collected from shooters' hands immediately after shooting. The secured material was examined with the use of SEM-EDX method in the automatic manner. The obtained results were expressed as frequencies of occurrence of particles assigned to various chemical classes. In order to establish the most discriminative of these features the Mann-Whitney test was performed. Cluster analysis was performed for grouping the analysed samples according to their origin, i.e. the type of ammunition. It has been found that samples of GSR originating from Browning 7.65 mm and Luger 9 mm ammunition can be fairly easy differentiated from the remaining samples, whereas samples of GSR originating from of Makarov 9 mm and these of Tokarev 7.62 mm could not be differentiated using frequencies of occurrence of particles in the selected chemical classes.     

The influence of a possible contamination of the victim's clothing by gunpowder residue on the estimation of shooting distance

A study was conducted to assess the influence of a possible contamination of the victim's clothing by gunpowder residue on the estimation of shooting distance. The study was focused on the scenario in which the contamination might be caused by the surface on which the shot victim could fall. Contamination of two types of textile was examined after contact with two types of surfaces. One round was fired above those surfaces (the line of firing parallel to the surface) prior to the contact. It was found that few gunpowder residue particles could be transferred to the clothing. These findings should be taken into account when interpreting results for shooting distance estimation in cases when a minute quantity of gunpowder residue particles is found around the bullet entrance hole.     

Gunshot residue particles formed by using ammunitions that have mercury fulminate based primers.

Ammunition having mercury fulminate-based primers are commonly manufactured by Eastern Bloc countries and used extensively in the Middle East. Gunshot residue (GSR) particles formed by firing these types of ammunition were examined. It was observed that much lower percentage of mercury-containing GSR particles were found in samples taken from a shooter as compared to the percentage of such particles in samples from cartridge cases. This fact must therefore be taken into account when interpreting case results. A plausible explanation for the results described is proposed.     

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.     

The Difficulties in Assessing Wounds Created by .410 Bore Ammunition and Weapons

When interpreting firearm injuries, the distinction between gunshot wounds and shotgun wounds is important, and separation of these categories is typically straightforward. However, .410 bore firearms can make the classification difficult. Shotguns and revolvers that can fire the same .410 bore ammunition are readily available. This study investigates the soot and gunpowder deposits and pellet patterning of these two types of weapons using cartridges specially designed for .410 bore revolvers and standard birdshot pellet ammunition. For both ammunition types, the revolver had more prompt pellet dispersion and positive detection of gunpowder at greater distances compared to the shotgun. Additionally, .410 bore slugs are of similar caliber to many common bullets. In comparing the .410 bore slugs to equivalent bullets, some morphologic differences may be imparted on the skin by the slugs, but the greatest insight into the weapon remained with the retained projectiles.     

An investigation on the secondary transfer of organic gunshot residues

Gunshot residues (GSR) are an important forensic trace in firearm-related events. Currently, routine GSR analyses focus on the detection and characterisation of the inorganic components (IGSR). The increasing prevalence of heavy metal-free ammunition challenges these current protocols and there is an increasing interest in how the organic components of GSR (OGSR) can provide complementary information. Similar to the situation with IGSR, OGSR compounds originally deposited on the shooter during the firing process may further be transferred onto another individual or surface. Hence, the aim of this study was to provide additional information regarding the risk of a secondary transfer of OGSR. Two scenarios were investigated, the first one related to the arrest process and the possibilities of a secondary transfer arising between a shooter onto a non-shooter (e.g. between a police officer and a person of interest (POI)). The second scenario concerned the transfer of OGSR onto the non-shooter after handling a firearm for few minutes without discharging it. One calibre was chosen, the .40 S&W calibre, used by several Australian State police forces. A secondary transfer was observed in all cases for the two scenarios investigated, for three compounds of interest: ethylcentralite (EC), diphenylamine (DPA), N-nitrosodiphenylamine (N-nDPA). The firearm handling scenario resulted in a larger secondary transfer to that of the arrest scenario. Overall, the amounts of OGSR detected on the non-shooter were generally lower than that detected on the shooter and controls after the arrest scenario. The results of this study provide complementary knowledge about OGSR, which can be further used to improve the current practice and the interpretation of OGSR evidence. In particular, it highlights that the secondary transfer proposition must be considered during the interpretation of forensic findings, especially when small amounts of OGSR target compounds are detected.     

Comparison of injuries caused by the pistols Tokarev, Makarov and Glock 19 at firing distances of 10, 15 and 25cm

Firings at cloth targets and at human skin from autopsy material were performed from the pistols 7.62 mm Tokarev (TT), 9 mm Makarov (PM) and 9 x 19 mm Glock 19 with common ammunition. The differences were in the soot deposit pattern, the degree of scorching of the synthetic fibres on the edges of the entrance hole and in the findings of the soot and the gunpowder particles. The results were similar on the cloth and on the skin targets. In the case of the TT and the PM, the soot deposit patterns reminded of a blossom or shafts of rays or fans, or the bullet wipe had four narrow and four wide sections regarding the number of lands and grooves. The TT left a large amount of soot and many gunpowder particles and caused the melting of the synthetic fibres on the edges of the entrance hole, producing a defect of the material 0.1-0.3 cm in diameter and defects of textile fibres around the entrance hole. In the skin the TT caused many intraepithelial tears, folds of the epidermis and recesses of the epidermis containing soot. Firings from the PM and the Glock 19 caused the melting only of the ends of individual synthetic fibres on the edges of the entrance hole. The PM left a large amount of soot and only a few gunpowder particles. The Glock 19 gave the least soot and the greatest number of gunpowder particles and also caused tears and recesses in the epidermis. Only in the case of the Glock 19, hexagonal or polygonal zones were seen in the soot deposit pattern. The differences in the soot pattern were more distinct at the firing distance of 10 cm. By increasing the distance from 10 to 15 cm, the intensity of soot diminished and began to disappear at 25cm, but remained more visible in the case of the TT. The gunpowder particles could be found in the epidermis and deeper in both layers of the dermis at all distances fired from the TT and the Glock 19. In the case of firings from the PM, at the distance 10 cm some of the gunpowder particles had penetrated into the dermis and most of them were in the upper layer of the dermis. At the firing distance of 15 and 25 cm, the gunpowder particles were only on and in the stratum corneum.     

A comparative study of gunshot residue originating from 9 mm Luger ammunition from various producers

Following previous work on differentiation between gunshot residue according to the type of ammunition used, a specific investigation was undertaken of traces originating from 9 mm Luger ammunition using SEM-EDX. The aim of this study was to determine whether GSR originating from this type of ammunition is similar, or whether differentiation could be made between particular manufacturers of Luger ammunition. The results were collected in the form of counts of particles in each of seven key elemental classes being combinations of lead, antimony and barium. These were then adjusted to a factor known as frequency of occurrence which allows comparison of the distribution of particles within the classes between samples with differences in absolute particle counts. The relationships between the samples were examined using non-parametric statistical tests: R-Spearman and tau-Kendall rank correlation coefficients. It has been found that most of the studied samples of GSR were similar to each other despite their originating from various manufacturers.     

Characterization of gunpowder samples using time-of-flight secondary ion mass spectrometry (TOF-SIMS)

Time-of-flight secondary ion mass spectrometry (TOF-SIMS) was utilized to obtain characteristic mass spectra from three different smokeless powders and six different black powder samples. In these mass spectra, peaks indicative of both the organic and inorganic additive constituents in the gunpowders were observed. TOF-SIMS was able to successfully differentiate between the different black and smokeless gunpowder samples analyzed with the aid of principal components analysis (PCA), a multivariate statistical analysis approach often used to reduce the dimensionality of complex data. TOF-SIMS was also used to obtain information about the spatial distribution of the various additives contained within the gunpowder samples. SIMS imaging demonstrated that that the samples could potentially be characterized by their 2-D structure, which varied from sample to sample. These results clearly demonstrate the feasibility of utilizing TOF-SIMS as a tool for the characterization and differentiation of gunpowder samples for general forensic applications.     

Development of a quantitative LC-MS/MS method for the analysis of common propellant powder stabilizers in gunshot residue

In traditional scanning electron microscopy/energy dispersive X-ray analysis of gunshot residue (GSR), one has to cope more and more frequently with limitations of this technique due to the use of lead-free ammunition or ammunition lacking heavy metals. New methods for the analysis of the organic components of common propellant powder stabilizers were developed based on liquid chromatography coupled to tandem mass spectrometry (LC-MS/MS). A multiple reactions monitoring scanning method was created for the screening of akardite II, ethylcentralite, diphenylamine, methylcentralite, N-nitrosodiphenylamine, 2-nitrodiphenylamine, and 4-nitrodiphenylamine, present in standards mixtures. Five out of seven of these target compounds can be selectively identified and distinguished from the two others with a high accuracy. Samples from the hands of a shooter were collected by swabbing and underwent solid phase extraction prior to analysis. Detection limits ranging from 5 to 115 mug injected were achieved. Results from several firing trials show that the LC-MS/MS method is suitable for the detection of stabilizers in samples collected following the firing of 9 mm Para ammunitions.     

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 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.     

Evaluation of the Simultaneous Analysis of Organic and Inorganic Gunshot Residues Within a Large Population Data Set Using Electrochemical Sensors*,†

The increasing demand for rapid methods to identify both inorganic and organic gunshot residues (IGSR and OGSR) makes electrochemical methods, an attractive screening tool to modernize current practice. Our research group has previously demonstrated that electrochemical screening of GSR samples delivers a simple, inexpensive, and sensitive analytical solution that is capable of detecting IGSR and OGSR in less than 10 min per sample. In this study, we expand our previous work by increasing the number of GSR markers and applying machine learning classifiers to the interpretation of a larger population data set. Utilizing bare screen-printed carbon electrodes, the detection and resolution of seven markers (IGSR; lead, antimony, and copper, and OGSR; nitroglycerin, 2,4-dinitrotoluene, diphenylamine, and ethyl centralite) was achieved with limits of detection (LODs) below 1 µg/mL. A large population data set was obtained from 395 authentic shooter samples and 350 background samples. Various statistical methods and machine learning algorithms, including critical thresholds (CT), naïve Bayes (NB), logistic regression (LR), and neural networks (NN), were utilized to calculate the performance and error rates. Neural networks proved to be the best predictor when assessing the dichotomous question of detection of GSR on the hands of shooter versus nonshooter groups. Accuracies for the studied population were 81.8 % (CT), 88.1% (NB), 94.7% (LR), and 95.4% (NN), respectively. The ability to detect both IGSR and OGSR simultaneously provides a selective testing platform for gunshot residues that can provide a powerful field-testing technique and assist with decisions in case management.