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.     

Transfer and Distribution of Gunshot Residue through Glass Windows

Research into the deposition patterns of primer gunshot residue (GSR) beyond a primary target was previously nonexistent. This study aimed to determine the deposition patterns of GSR once a bullet passed through an initial target and continued on its path into additional targets. Multiple repetitions were performed to assess the GSR deposition patterns after a bullet was shot through a closed window into either a dummy or a wall within an enclosed room. Samples were taken from both the primary and secondary target holes as well as from nontarget areas. Significant amounts of GSR were found on all samples. The results show that GSR continues to be deposited along the path of the bullet after passing through a primary glass target. These findings reiterate the lack of probative value in collecting GSR samples from gunshot victims even if they are in an enclosed area separate from the shooter.     

Discharge of a Pistol Out a Car Window with the Breech Within the Interior of the Car: Analysis of Gunshot Residue on a Car's Interior Surfaces

The defendant, the driver of the questioned car, allegedly extended his right arm over the passenger seat and fired a single shot from a 380 pistol out the passenger window with the pistol's breech within the car. A simulation of this shooting scenario using the same model car, but different year, was conducted to quantitate gunshot residue (GSR) contamination of interior surfaces within the car. The test car's dash and headliner/window frame above the pistol had the heaviest GSR contamination. The dash GSR from airborne deposition documents a firearm discharge within the vehicle. Transfer from GSR‐contaminated hands or clothing to the dash is unlikely. The heavy GSR contamination of the headliner/window frame above the pistol likely documents the window from which the pistol was fired, but additional experiments are needed to verify.     

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.     

Automated SEM/EDS Analysis of Airbag Residue. II: Airbag Residue as a Source of Percussion Primer Residue Particles

Abstract:  Automated scanning electron microscopy with energy dispersive spectroscopy has been used to analyze airbag residue particles. Analysis of airbag residue from some passenger side airbags revealed some residue particles which are consistent with gunshot residue (GSR) samples. The source of these particles was determined to be percussion primers used to initiate the chemical reaction for deployment. This article identifies some vehicles which contain this type of airbag and demonstrates the types of particles which could be misidentified as being GSR. The low numbers of GSR particles in among the large particle populations of zirconium and/or copper–cobalt particles, which are clearly airbag residue, allow the trained analysts to distinguish the correct source of this residue. Particles containing high aluminum levels, elevated levels of allowable elements in GSR particles, or the presence of elements that are rare in GSR particles stand out as indications that the particles are not GSR in origin. This study serves as a guide to analysts who perform particle analysis in forensic investigations.     

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.     

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.     

Analysis of Gunshot Residue and Associated Materials—A Review

Abstract: A comprehensive review of the scientific literature on gunshot residue (GSR) is presented. Aspects of both inorganic and organic GSR are discussed, from formation and distribution, to sample collection, preparation, and analysis using a variety of techniques. The interpretation of GSR results is also considered including issues surrounding the contamination, distribution, and transfer of GSR. Potential problems with ulterior sources of GSR like particles have been reported in the literature. For example, particles from environmental and occupational sources have been highlighted as exhibiting similar chemical and morphological characteristics to GSR. These findings are put into context with regard to interpreting samples. A move toward a “case by case” approach is argued to be more preferable to a “formal” classification system where possible. The analysis of both inorganic and organic compositions of residue samples as well as morphological considerations is considered to be a more ideal approach to GSR analysis, whereever practicable.     

Gunshot residue in Chicago police vehicles and facilities: an empirical study

Suspects in shooting investigations in Chicago are routinely transported in department vehicles and detained in department facilities prior to gunshot residue (GSR) evidence collection. The GSR test results are used to associate the suspect with primary exposure to GSR. The potential for these vehicles and facilities being sources of secondary GSR contamination needed to be determined. A total of 201 samples were collected from randomly selected vehicles and detention facilities. The sampling collected trace materials from surfaces that suspects' hands may contact during the arrest process. These samples were examined for the presence of GSR particles using scanning electron microscopy. Upon completion of the automated analysis, those particles that met an initial GSR screening criterion were relocated and reanalyzed. The locations where GSR particles were recovered allowed us to make recommendations to the Chicago Police Department with regard to transporting and detaining these suspects. The low number of GSR particles recovered suggests that the potential for secondary contamination, although present, is relatively low.     

Detection of Gunshot Residue in Blowfly Larvae and Decomposing Porcine Tissue Using Inductively Coupled Plasma Mass Spectrometry (ICP‐MS)*

Abstract: Blowfly larvae and porcine tissue contaminated with gunshot residue (GSR) were collected during summer and winter months, over a 37‐day and a 60‐day sampling period, respectively. Wound samples were microwave‐digested and analyzed by inductively coupled plasma mass spectrometry (ICP‐MS) for the detection of antimony, barium, and lead. During summer, the 37‐day sampling period encompassed all stages of decomposition, except skeletonization. The three elements were detected in larvae only on days 3 and 4 after death but were detected at significant levels in tissue samples throughout the entire sampling period. In winter, no significant decomposition was observed throughout the 60‐day sampling. Although temperatures were too low for blowfly activity, the three elements were detected in the tissue samples at relatively constant, significant levels. Hence, GSR determination in tissue was more dependent on decomposition stage rather than time since death.     

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.     

Electrical Pulse Generated Upon Discharging a Firearm and Its Implication for Gunshot Residue Analysis

Ammunition primers consisting of a mixture of lead styphnate, barium nitrate, and antimony (III) sulfide, upon deflagration, lead to the formation of inorganic gunshot residue (GSR). The cations, from their predeflagration form, undergo reduction reactions during burning to form the classic spheroidal, micron-sized particles indicative of GSR. However, the rapidly changing pressure and temperature of the reaction zone implies that the reactions cannot go to completion. In this study, we use a conductivity detector to show that GSR produces an electrical pulse which corroborates the incomplete redox chemistry. We find that the shape of some GSR formed in an electric field also suggests its nonneutral character. Tantalizingly, the formation of GSR might be a result of Coulombic repulsion shattering the molten droplets in to smaller spheroids. Lastly, we suggest that deposition or transfer of GSR could be influenced by static electricity, an area which should be further studied.     

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.     

Lead-free primer residues: a qualitative characterization of Winchester WinClean, Remington/UMC LeadLess, Federal BallistiClean, and Speer Lawman CleanFire handgun ammunition

The elemental composition and postfiring residues of several "lead-free" or "nontoxic" centerfire handgun ammunition types currently available to the general public were examined. Offerings from Winchester, Remington/UMC, Federal and Speer were obtained from retail sources in both .45 ACP and 9 mm when possible. A total of 112 postfiring residue samples (SEM pins) were collected at varying distances from the muzzle, at two distances from target and from the shooter's hands. An additional 20 samples were collected by direct ignition of primers. Qualitative determinations were carried out using scanning electron microscopy (SEM)/electron dispersive spectrometry (EDS) analysis. All types tested contained aluminum (Al), silicon (Si), copper (Cu), and zinc (Zn). Most contain traces of sulfur and calcium. Winchester WinClean and Remington LeadLess contained potassium as the principle ingredient. Federal BallistClean contained barium, while Speer Lawman CleanFire contained strontium. In the main, these compared favorably with manufacturers' MSDS publications and patents granted. The characterizations undertaken here will be of use to the forensic electron microscopist as these formulations gain popularity.     

Automated SEM/EDS Analysis of Airbag Residue.* I: Particle Identification

Abstract: Deployed airbags can be a valuable source of probative forensic materials. During an accident, trace evidence can be deposited on the airbag cover and in addition, the residue produced by the gas generation system is released into the passenger compartment of the vehicle as the airbag deflates. This residue can be used to associate a suspect with the vehicle at the time of the accident. This study identifies particles containing zirconium, strontium, and/or copper–cobalt along with other elements from the gas generation systems and aluminum silicon microfibers from airbag filters as the probative material which may be produced and deposited on a suspect’s hands and/or clothing. Scanning electron microscopy can be used to identify this metallic residue. Modification of the search criterion used for gunshot residue analysis allows for automated analysis of the samples. Proper collection of the airbag standard is essential to identify which materials were produced. Prompt collection of suspect samples allows the analysts the ability to make the proper identifications and associations. This analytical technique can be a probative tool in criminal investigations.     

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.     

Scanning Electron Microscope Analysis of Gunshot Defects to Bone: An Underutilized Source of Information on Ballistic Trauma

Recent years have seen increasing involvement by forensic anthropologists in the interpretation of skeletal trauma. With regard to ballistic injuries, there is now a large literature detailing gross features of such trauma; however, less attention has been given to microscopic characteristics. This article presents analysis of experimentally induced gunshot trauma in animal bone (Bos taurus scapulae) using full metal jacket (FMJ), soft point (SP), and captive bolt projectiles. The results were examined using scanning electron microscopy (SEM). Additional analysis was conducted on a purported parietal gunshot lesion in a human cranial specimen. A range of features was observed in these samples suggesting that fibrolamellar bone response to projectile impact is analogous to that observed in synthetic composite laminates. The results indicate that direction of bullet travel can be discerned microscopically even when it is ambiguous on gross examination. It was also possible to distinguish SP from FMJ lesions. SEM analysis is therefore recommended as a previously underexploited tool in the analysis of ballistic trauma.     

Pyrotechnic reaction residue particle analysis

Pyrotechnic reaction residue particle (PRRP) production, sampling and analysis are all very similar to that for primer gunshot residue. In both cases, the preferred method of analysis uses scanning electron microscopy to locate suspect particles and then uses energy dispersive x-ray spectroscopy to characterize the particle's constituent chemical elements. There are relatively few times when standard micro-analytical chemistry performed on pyrotechnic residues may not provide sufficient information for forensic investigators. However, on those occasions, PRRP analysis provides a greatly improved ability to discriminate between materials of pyrotechnic origin and other unrelated substances also present. The greater specificity of PRRP analysis is the result of its analyzing a large number of individual micron-sized particles, rather than producing only a single integrated result such as produced using standard micro-analytical chemistry. For example, PRRP analyses are used to demonstrate its ability to successfully (1) discriminate between pyrotechnic residues and unrelated background contamination, (2) identify that two different pyrotechnic compositions had previously been exploded within the same device, and (3) establish the chronology of an incident involving two separate and closely occurring explosions.     

Evaluation of Total Nitrite Pattern Visualization as an Improved Method for Gunshot Residue Detection and its Application to Casework Samples

Visualization of nitrite residues is essential in gunshot distance determination. Current protocols for the detection of nitrites include, among other tests, the Modified Griess Test (MGT). This method is limited as nitrite residues are unstable in the environment and limited to partially burned gunpowder. Previous research demonstrated the ability of alkaline hydrolysis to convert nitrates to nitrites, allowing visualization of unburned gunpowder particles using the MGT. This is referred to as Total Nitrite Pattern Visualization (TNV). TNV techniques were modified and a study conducted to streamline the procedure outlined in the literature to maximize the efficacy of the TNV in casework, while reducing the required time from 1 h to 5 min, and enhancing effectiveness on blood‐soiled samples. The TNV method was found to provide significant improvement in the ability to detect significant nitrite residues, without sacrificing efficiency, that would allow for the determination of the muzzle‐to‐target distance.     

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.