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.     

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.     

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.     

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.     

Differential pulse anodic stripping voltammetry of lead and antimony in gunshot residues

Differential pulse anodic stripping voltammetry (DPASV) using a glassy carbon/mercury film electrode (GC/MFE) has been applied for characterization and quantitative detection of gunshot residues (GSR). This technique allows for simultaneous detection of Pb and Sb from GSR hand swabs that is simple, fast, and non-destructive. The use of a KNO₃/hydrazine sulfate matrix, instead of HCl, reduces possible interferences and allows for a small sample size to be used in analysis but yielding greater sensitivity.     

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.     

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.     

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.     

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.     

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).     

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.     

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.     

Particle Analysis for the Detection of Gunshot Residue (GSR) in Nasal Samples Using Scanning Laser Ablation and Inductively Coupled Plasma-Mass Spectrometry (SLA-ICPMS)

Currently, aluminum stub with carbon adhesive devices are used to collect inorganic gunshot residues (GSR) from the hands of a shooter. In an ideal shooting case, the gunshot particles do not persist for more than 2 h in the hands of the shooter, provided that the hands have not been washed. However, for forensic analysis and inference, the extended persistence of GSR would be desirable. This study investigates a novel GSR sampling and detection protocol. Sampling was performed in the nostrils using swab devices impregnated in ethylenediaminetetraacetic acid (EDTA). The GSRs persisted for longer periods in nasal mucus than on the hands, and particles were detected 6 h after shooting occurred. The analytical determination was conducted by scanning laser ablation-inductively coupled plasma-mass spectrometry (SLA-ICPMS) which enable the identification of the number of particles and their elemental composition. Seventeen isotope signals corresponding to ¹³C, ²⁰⁵Tl and 15 analytes that are usually associated with the composition of GSR residues were monitored: ²⁷Al, ²⁹Si, ³¹P, ³³S, ³⁵Cl, ³⁹K, ⁴⁴Ca, ⁵⁷Fe, ⁶⁰Ni, ⁶³Cu, ⁶⁶Zn, ¹¹⁸Sn, ¹²¹Sb, ¹³⁷Ba, and ²⁰⁸Pb. The SLA technique enabled the reduction of the swab analysis time to 40 min. The effectiveness of this methodology was evaluated with two types of firearms: a pistol and a shotgun. The results indicated that the methodology proposed for the analysis of the nasal GSR was effective and that it can improve or complement the forensic analyses and inferences presented in a court.     

A study of dispersion of gunshot residue from a frequently used Serbian ammunition cal. 7.65 mm to support selected aspects of casework in North Macedonia

The subject of this research was the inorganic gunshot residue component collected from shooting patterns obtained on woven cotton cloth using a Pietro Beretta model 70 pistol, cal. 7.65 mm and Serbian ammunition for the following muzzle-to-target distances: 25, 50, 75, 100 and 125 cm. For each distance, three rounds of shooting were performed. Particles were lifted within a 10 cm radius of the projectile entrance and automatically analyzed using a scanning electron microscope coupled with an energy dispersion X-ray spectrometry. The obtained data on the populations of particles were analyzed taking into account their numbers, chemical classes and sizes. The results showed an apparent maximum incidence within all particles containing barium at about 50 cm distance. Also, lead particles revealed a distinct behaviour, being dominant at a 25 cm distance, falling below the other chemical classes, and finally becoming dominant again at 125 cm. The analysis of the frequency of occurrence of particles sorted according to their sizes confirmed that the small particle population is the largest, and their distribution in function of the equivalent circle diameter is exponential-like. The obtained results provided knowledge on the distribution of particles in the vicinity of the tested firearm and ammunition cal. 7.65 mm which generally corroborates with similarly studied GSR distributions obtained for the use of pistols cal. 9 mm. This information, together with the examinations of gunshot damages and other types of residues such as soot or unburned propellant grains may support qualitative inferences on shooting distance estimation, especially in cases, when the firearm and cartridges are not available to perform test shooting. In such cases even roughly estimated shooting distance can be helpful, e.g. for confirming or excluding the possibility of self-inflicted injuries or suicide and infer on the mutual position of the shooting stage actors. An example of casework that illustrates intermediate shooting distance estimation is presented.     

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.     

The Effect of Skin Debris on Gunshot Residue Sampling and Detection

These experiments were designed to determine whether skin debris (desquamated epithelial cells and apparent skin oils) affects gunshot residue (GSR) particle detection on the sticky tape lift samples prepared for scanning electron microscopy (SEM). A dabbing experiment showed that GSR particles accumulate not only on the adhesive surface of the sampler, but also on the epithelial cell surfaces. Samplers were loaded with target GSR followed by dabbing 30 times on the back of a hand. Backscatter electron images were taken at 20 kV and for some at 30 kV of the same areas. The samplers were then treated with a sodium/calcium hypochlorite solution (bleach) to remove skin debris and again imaged in the SEM. Comparison of these images shows more GSR particles will likely be revealed at 30 kV than 20 kV and more particles revealed by the bleach treatment in an automated SEM system.     

A Study of Background Levels of Antimony,Barium, and Lead on Vehicle Surface Samples by Graphite Furnace Atomic Absorption

Law enforcement agencies routinely sample for gunshot residue (GSR) by bulk techniques and often submit swabs taken from other surfaces besides the hands of the suspect shooter. This study aims to establish the prevalence of antimony, barium, and lead on normally handled automobile surfaces by graphite furnace atomic absorption analysis. No positives were determined on 50 sampled automobile surfaces above cutoff (positive) from background levels. Transfers of GSR particles from shooter hands to automobile surfaces were found to potentially allow for positive GSR determinations, but such transfers seem to be dependent on the shooting conditions and length of GSR exposure. We determined that our bulk analysis method yields an overall 87.94 ± 5.52% extraction efficiency from cotton swabs, while the LOQ determinations strengthening the fact that bulk analysis methods are valid and valuable tools for GSR investigations.     

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.     

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.