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: Recreational Shooter Vehicle Distribution

The susceptibility for recreational shooters to transfer gunshot residue (GSR) to both the interior and exterior of a vehicle is investigated. A comprehensive sampling protocol was used to assess the most likely areas of GSR transfer from recreational shooter contact, such as the steering wheel and the area, the firearms were stored (the trunk). Up to 315 characteristic GSR, particles were found in several locations throughout the interior of a vehicle. As many as 876 characteristic particles were found throughout a single vehicle. The data indicate that vehicles frequently occupied by firearms users are a potential source for inadvertent transfer of GSR to persons unrelated to firearm activity. In criminal cases where vehicles have been used, such transfer processes for GSR need to be considered within the context of any case interpretation. The implications for subsequent contamination and transfer processes from such vehicles require further investigation.     

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.     

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.     

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 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.     

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.     

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.     

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.     

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.     

Elemental Characterization and Discrimination of Nontoxic Ammunition Using Scanning Electron Microscopy with Energy Dispersive X‐Ray Analysis and Principal Components Analysis

Concerns over the toxic by‐products produced by traditional ammunition have led to an increase in popularity of nontoxic ammunition. In this work, the chemical composition of six brands of nontoxic ammunition was investigated and compared to that of a road flare, which served as an environmental source with similar composition. Five rounds of each brand were fired while a further five were disassembled and the primer alone was fired. Particles collected from all samples, including the road flare, were analyzed by scanning electron microscopy with energy dispersive X‐ray analysis. Common elements among the different ammunition brands included aluminum, potassium, silicon, calcium, and strontium. Spectra were then subjected to principal components analysis in which association of the primer to the intact ammunition sample was generally possible, with distinction among brands and from the road flare sample. Further, PCA loadings plots indicated the elements responsible for the association and discrimination observed.     

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.     

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.     

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.     

A Fatal Shot with a Signal Flare—A Crime Reconstruction*

Abstract: A reconstruction of an incident of a fatal wounding of a football fan with a parachute flare was performed. Physical and chemical examinations of the victim’s trousers and parts of a flare removed from the wound in his leg were performed by means of an optical microscope and a scanning electron microscope coupled with an energy dispersive X‐ray spectrometer. Signs of burning were seen on the front upper part of the trousers, including a 35–40 mm circular hole with melted and charred edges. Postblast residue present on the surface of the trousers contained strontium, magnesium, potassium, and chlorine. Also the case files—the medical reports and the witnesses’ testimonies—were thoroughly studied. It has been found that the evidence collected in the case supported the version of the victim being shot by another person from a distance.     

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.     

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.     

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.     

Analysis of Luminescent Gunshot Residue (LGSR) on Different Types of Fabrics

The collection of gunshot residue on fabric can be an arduous task due to the microscopic size of particles (blind collection) and sheddability of some fabrics. The introduction of luminescent markers and consequent formation of luminescent gunshot residue (LGSR) can facilitate this analysis. In this study, different fabrics were analyzed in order to verify the persistence of the LGSR on them, the possibility of collecting and analyzing particles by video spectral comparator (VSC) and SEM/EDS. Also, different colored fabrics were used as targets in order to investigate influence of fabric color on LGSR visualization. Furthermore, the influence of the fabric type in the distribution of the LGSR deposited around the projectile´s hole entrance was evaluated. The fabric sheddability did not alter collection of the particles or analysis. It was possible to observe and collect LGSR on all tested fabrics, even after the fabric had been shaken, or in colored fabrics.     

The Analysis of Gun‐Cleaning Oil as Long‐Distance Gunshot Residue and Its Implications for Chemical Tags on Bullets

Using a BB gun, it was shown that a gun‐cleaning oil (GCO) can be wiped from the barrel by a projectile and carried much longer distances than those usually associated with solid gunshot residue (GSR). Analysis of GCO subsequently deposited on a target was performed using pentane extraction and gas chromatography. (Hoppe's GCO was used here as a model.) When a 0.45 caliber handgun was used, analysis reveals that most of the GCO wiped from the barrel does not survive, owing to the elevated temperatures encountered. However, two components of the GCO, a long‐chain fatty acid and its ethyl ester, do survive and can be detected in the bullet wipe. This suggests that GCO may be considered as GSR, uniquely detectable at long distances, and that other chemical compounds could either be added to a GCO or directly to bullets, to serve as identifying chemical tags.