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.     

Time periods of GSR particles deposition after discharge-final results

The elemental objects of the research study are: determination of time periods corresponding to gunshot residue particles (GSR) deposition after the shot from selected pistols and a revolver, and evaluation of the deposited particles number. For several shooting experiments were used a pistol CZ model 85, caliber 9 mm Luger with common ammunition 9 mm Luger FMJ Sellier & Bellot, a pistol CZ model 70, caliber 7.65 mm Browning (32 ACP) with common 7.65 mm Browning FMJ Sellier & Bellot ammunition and a revolver S&W Modell 60, barell length 2-1/8', cal. .38 Special with common Sellier&Bellot (FMJ) ammunition. The results of the study have indicated the behavior of GSR particles deposited after a single discharge. The overall time interval of GSR particles deposition and the number of deposited particles with the above mentioned arms and ammunition were established. The results can potentially be used for clarifying the situation at crime scenes and for subsequent interpretation of GSR evidential value in caseworks.     

Distribution of lead and barium in gunshot residue particles derived from 0.22 caliber rimfire ammunition.

0.22 caliber rimfire ammunition is commonly encountered in firearms incidents in Australia. This paper reports on work which has confirmed the nonhomogeneous nature of gunshot residue (GSR) particles and that the lead and barium distribution within particles varies significantly with the particle size and structure. The outcome has been an improved understanding of how the particle formation influences the ability to determine the origin of GSR derived specifically from 0.22 caliber rim fire ammunition.     

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.     

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.     

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.     

Identification of gunshot residue: a critical review

A review of the scientific papers published on inorganic gunshot residue (GSR) analysis permits to study how the particle analysis has shown its capability in detection and identification of gunshot residue. The scanning electron microscope can be the most powerful tool for forensic scientists to determine the proximity to a discharging firearm and/or the contact with a surface exposed to GSR. Particle analysis can identify individual gunshot residue particles through both morphological and elemental characteristics. When particles are detected on the collected sample, the analytical results can be interpreted following rules of a formal general interpretative system, to determine whether they come from the explosion of a primer or from other possible sources. The particles on the sample are compared with an abstract idea of "unique" GSR particle produced by the sole source of the explosion of a primer. "Uniqueness" is not the only problem related to GSR detection and identification for a forensic scientist. With "not-unique" particles interpretation of results is extremely important. The evidential strength of "not-unique" particles can increase with a more fruitful interpretative framework based on Bayes rule. For the assessment of the value of a GSR in linking a suspect and a crime, it is important to compare two hypothesis: the first can be that of the evidence if the suspect has been shooting in a specific situation, the second that of the evidence if the suspect was not involved in this shooting. This case specific or case-by-case approach is closer to what the court is interested in. The authors consider that a "case-by-case" approach should be followed whenever possible. Research of models and data such as those developed in other trace evidence material (fibres, glass, etc.) using a Bayesian approach is suggested in the interpretation of GSR.     

Analysis of gunshot residue test results in 112 suicides

The results of gunshot residue (GSR) tests in 112 suicide cases investigated by the U.S. Army Criminal Investigation Command over a ten-year period are described. Only suicide cases in which there was certainty that the victim fired a weapon were examined in an effort to reduce ambiguous results. Previous case work research by Rudzitis indicated that positive GSR test results were encountered in suicides 62% of the time using various combinations of neutron activation analysis (NAA) and atomic absorption spectrophotometry (AAS). Threshold values of 0.2-micrograms antimony and 0.3-micrograms barium (0.2-micrograms antimony and 0.5-micrograms barium after 1985) used by the U.S. Army Criminal Investigation Laboratory resulted in positive GSR results in suicide cases 38% of the time. The effects of time, location of body, handling of the body, weapon type, caliber, and condition of the hands on GSR results are examined. Case studies involving suicides by unit armorers are discussed.     

Handguns and ammunitions indicators extracted from the GSR analysis

The computer automated scanning electron microscope. X-ray microanalysis of Firearms Discharge Residue (FDR) can reveal substantial information about the circumstances of their generation beyond the presence of characteristic gunshot residue (GSR). Indicators of the type of weapon and ammunition used can he obtained from the distribution of GSR particle shapes and from the multi-element analysis of the FDR sample. This is demonstrated for a large database of GSR samples from nine different handguns and over 60 different ammunitions. An example classification scheme is presented for the supporting particles generally found present in FDR. When particle type area concentration ratios are normalized to the iron (Fe) particle type, results show it is possible to distinguish much about the metal used in the weapon manufacture, whether it was of large or small caliber, whether the bullets were jacketed or plated, and whether the cartridge cases were of aluminum, brass, or nickel-plated brass. Standardization of such analytical schemes would be advantageous.     

Characterisation of 0.22 caliber rimfire gunshot residues by time-of-flight secondary ion mass spectrometry (TOF-SIMS): a preliminary study

The application of time-of-flight secondary ion mass spectrometry (TOF-SIMS) for the characterisation of gunshot residue (GSR) from 0.22 caliber rimfire ammunition is reported. Results obtained by TOF-SIMS were compared with conventional scanning electron microscopy (SEM) studies. As could be expected, TOF-SIMS exhibited greater elemental sensitivity than SEM equipped with energy dispersive X-ray detection (SEM-EDX), and was also capable of detecting fragments characteristic of inorganic compounds. This preliminary study indicates that TOF-SIMS offers substantial potential for forensic GSR examinations as a complementary technique to SEM-EDX. In addition TOF-SIMS is applicable to the analysis of individual particles in the typical size range encountered in GSR casework.     

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.     

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.     

Rapid search and quantitative analysis of gunshot residue particles in the SEM

Automated scanning electron microscopy coupled with image analysis and X-ray micro analysis was used to characterize a variety of gunshot residue (GSR) samples. More than 500 rounds of commercially available ammunition and six different types of hand gulls were used in the study of 17 GSR and 19 reference specimens. The individual particle X-ray composition was determined for 12 different elements. Elemental composition of GSR particles was highly variable but consistent with compounds mixed into or associated with a barium oxide matrix. When present in a specimen, GSR could be adequately characterized with automated procedures in less than an hour by restricting analyses to features larger than 2 microm. In "clean" samples, a higher resolution particle search was required to avoid reporting false negatives. Careful control of the back scattered electron signal strength threshold, by reference to a standard, was needed to ensure both time-efficient and accurate analyses. Samples collected from non-shooting subjects. active in a physical environment which contained firearms discharge residue were seen to be easily contaminated by sub-micron GSR particles.     

Detection of Gunshot Primer Residue on Bone in an Experimental Setting—An Unexpected Finding*

Abstract: Pork ribs with intact muscle tissue were used in an experimental attempt to identify bullet wipe on bone at distances from 1 to 6 feet with 0.45 caliber, full metal jacket ammunition. This resulted in the unexpected finding of primer‐derived gunshot residue (GSR) deep within the wound tract. Of significance is the fact that the GSR was deposited on the bone, under the periosteum, after the bullet passed through a Ziploc^® bag and c. 1 inch of muscle tissue. It is also important to note that the GSR persisted on the bone after the periosteum was forcibly removed. The presence of primer‐derived GSR on bone provides the potential to differentiate gunshot trauma from blunt trauma when the bone presents an atypical gunshot wound. In this study, the presence of gunshot primer residue at a distance of 6 feet demonstrates the potential for establishing maximum gun‐to‐target distance for remote shootings.     

Fate and Behavior of Gunshot Residue—A Review

A review of the literature concerning the fate and behavior of gunshot residue (GSR) is presented. A number of concomitant parameters including firearm and ammunition type, plume and GSR material characteristics, travel distances, chemical composition and GSR morphology are critically discussed in relation to their effects on the distribution and deposition, transfer and persistence processes of GSR. The underlying mechanisms associated with such processes are also considered. Knowledge of these processes on GSR materials could provide valuable information concerning scene preservation and subsequent forensic sampling. The number of GSR particles deposited can vary significantly with each firearm discharge, highlighting the potential to produce distinctive data in each individual case. With the continual development and compositional changes of new ammunition types, further evaluation of the effect these processes may have on GSR evidence and their possible influence on the interpretation of the analytical results should be given due consideration.     

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.     

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.     

Forensic veterinary radiology: ballistic-radiological 3D computertomographic reconstruction of an illegal lynx shooting in Switzerland

The most popular handgun in Brazil is the single round-barrel caliber 0.38 revolver. In recent years, however, owing to the modernization of police arms and their availability on the legal and illicit markets, pistols have become increasingly popular and currently represent about 20% of police seizures. In a previous paper we presented a novel collection method for gunshot residues (GSR) using a sampling procedure based on ethylenediamine-tetraacetic acid (EDTA) solution as a complexing agent on moistened swabs with subsequent detection using sector field-high resolution-inductively coupled plasma-mass spectrometry (SF-HR-ICP-MS). In the present paper, we discuss the capability of this methodology to identify antimony (Sb), barium (Ba) and lead (Pb) on the hands of volunteers after shot tests with 9 mm and 0.40 in. caliber pistols. Two types of munitions were tested: 9 mm Taurus and clean range. The use of a technique with high sensitivity, such as SF-HR-ICP-MS, permits the identification of low concentrations (less than 1 microg/L) of metals in firearm residue and constitutes a powerful tool in forensic science. We also discuss the importance of the sampling procedure, including collection from a different body part than the gun hand of the suspect. Comparison of the analytical data obtained allows clear discrimination between samples from the hands of shooters and non-shooters.     

Comparison of GSR Composition Occurring at Different Locations Around the Firing Position

Abstract: Variations in gunshot residue (GSR) compositions are used in the reconstruction of shooting incidents. In this study, GSR samples taken from seven different locations around and in the firearm were collected and analyzed using scanning electron microscopy/energy dispersive X‐ray analysis. Four different types of ammunition were applied. Very low correlations were found when different ammunition were used. This clearly shows that it is possible to differentiate between ammunition types. When the same ammunition was used, high correlations were found between samples taken from external positions (such as hands of shooter, bullet‐entrance holes) but poor correlation was found between internal samples (such as firearm barrel, cartridge case) and external samples. A high degree of association was found between samples that simulated victim and shooter. These findings clearly demonstrate that GSR comparison studies are meaningful but care needs to be taken when choosing suitable exhibits. External samples (such as hands of shooter, bullet‐entrance holes) are more suitable candidates than internal samples (barrel of the firearm, cartridge case).     

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.