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.     

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

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

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.     

An investigation on the secondary transfer of organic gunshot residues

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

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.     

Investigating the effect of changing ammunition on the composition of organic additives in gunshot residue (OGSR)

The measurement of the organic additives in smokeless gunpowder is an attractive approach for the detection of handgun use because it provides compositional information that can help associate residues and unfired gunpowder. We investigate several factors that will be required to advance the characterization of organic gunshot residue (OGSR) as a useful forensic tool, including evaluating residue contamination from previously fired ammunition, particle-to-particle compositional variability, and compositional features resulting from the type of firing primer used. Using ammunition loaded with known smokeless powders containing different stabilizers, a sequence of shots was fired from a .357 magnum revolver, and the muzzle exit residues were collected. Compositional analysis of the residues, both in bulk and as single particles, showed only a trace of the previously fired powder in the first shot and none in subsequent shots. In an additional experiment testing conventional leaded and the new lead-free firing primers, the OGSR composition was found not to depend on the primer type.     

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 preliminary investigation into the use of FTIR microscopy as a probe for the identification of bullet entrance holes and the distance of firing

FTIR spectroscopy has been found to be a valuable probe for the analysis of the distribution of organic components such as nitroglycerine in gunshot residues deposited on and around the bullet entrance hole of the clothing of the victim in short range firearm discharges. The method can be utilised for the detection and estimation of organic gunshot residues (OGSR) on the hands and clothing of the shooter. The method is specific and sensitive and is likely to be free from interference from, for example, environmental pollution. The method shows potential to be utilised as a suitable alternative to the widely used SEM-EDX analysis of the total contents of lead, barium and antimony present in the gunshot deposits around the bullet entrance hole. The method was tested in the laboratory and the results were validated by Gas Chromatography-Mass Spectrometry (GC-MS).     

A simple method for detection of gunshot residue particles from hands, hair, face, and clothing using scanning electron microscopy/wavelength dispersive X-ray (SEM/WDX).

We devised a simple and rapid method for detection of gunshot residue (GSR) particles, using scanning electron microscopy/wavelength dispersive X-ray (SEM/WDX) analysis. Experiments were done on samples containing GSR particles obtained from hands, hair, face, and clothing, using double-sided adhesive coated aluminum stubs (tape-lift method). SEM/WDX analyses for GSR were carried out in three steps: the first step was map analysis for barium (Ba) to search for GSR particles from lead styphnate primed ammunition, or tin (Sn) to search for GSR particles from mercury fulminate primed ammunition. The second step was determination of the location of GSR particles by X-ray imaging of Ba or Sn at a magnification of x 1000-2000 in the SEM, using data of map analysis, and the third step was identification of GSR particles, using WDX spectrometers. Analysis of samples from each primer of a stub took about 3 h. Practical applications were shown for utility of this method.     

Firework displays as sources of particles similar to gunshot residue

In light of past research being targeted to find specific particles which may be similar to gunshot residue (GSR), this project was formulated to detect any possible particulate by random particle fallout onto substrates at firework displays and to assess the impact this may have on GSR evidence. Firework residue was collected at a display site, from amongst spectators as well as from the author's hair 90min after the display. SEM-EDX analysis has detected such particulate in all three scenarios, with the firework particle population at large providing a solid ground for discrimination from GSR. Wind dispersal was found to decrease the particle population and subsequently, the latter's discriminatory power. Some particles, if treated individually were found to be indistinguishable from GSR. Findings also include residues which may mimic strontium based GSR as well as GSR which may be mixed with that from previous firings. The continuous changes made to primer and propellant compositions by manufacturers also call for greater consideration when classifying particles as originating from pyrotechnic devices. Furthermore, authorities such as police forces should be made more aware about the incidence of such particle transfer in firework related periods.     

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.     

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

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

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.     

Preliminary evaluation of the persistence of organic gunshot residue

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

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.     

Characterisation of gunshot residue from three ammunition types using suppressed anion exchange chromatography

Gunshot residue (GSR) is commonly analysed in forensic casework using either scanning electron microscopy with energy-dispersive X-ray spectroscopy (SEM-EDX) or gas chromatography-mass spectrometry (GC-MS). Relatively little work has been reported on the post-discharge GSR content of non-metallic inorganic or low molecular weight organic anions to distinguish between different ammunition types. The development of an analytical method using suppressed micro-bore anion exchange chromatography (IC) is presented for the analysis of GSR. A hydroxide gradient was optimised for the separation of 19 forensically relevant organic and inorganic anions in <23min and sensitivities of the order of 0.12-3.52ng of anion detected for all species were achieved. Along with an optimised extraction procedure, this method was applied to the analysis of post-ignition residues from three selected ammunition types. By profiling and comparing the anionic content in each ammunition residue, the possibility to distinguish between each type using their anionic profiles and absolute weight is presented. The potential for interference is also discussed with respect to sample types which are typically problematic in the analysis of GSR using SEM-EDX and GC-MS. To the best of our knowledge this represents the first study on the analysis of inorganic anions in GSR using suppressed ion chromatography.     

Brake linings: a source of non-GSR particles containing lead,barium, and antimony

The observation of environmental particles similar in composition to gunshot residue (GSR) are not new to forensic experts and have been described in the scientific literature. In order to better define the origin of these particles, brake linings and their wear products were examined by SEM-EDX. The results obtained demonstrate that some types of brake linings contain lead, barium, and antimony and that they can represent a source of particles showing GSR-like elemental profiles. Most of these particles can be easily discriminated from primer discharge residue because of the high levels of iron or the presence of "prohibited" elements in the spectrum. However, particles with iron at minor or trace levels and lacking "prohibited" elements were also found. It is thus advisable to use caution when describing the composition of similar particles as "unique" to primer discharge residue. The strict application of a rigorous morphological criterion is also recommended.     

Gunshot residue testing in suicides: Part I: Analysis by scanning electron microscopy with energy-dispersive X-ray

Several different methods can be employed to test for gunshot residue (GSR) on a deceased person's hands, including scanning electron microscopy with energy-dispersive x-ray spectroscopy (SEM-EDX) and inductively coupled plasma-atomic emission spectrometry (ICP-AES). Each of these techniques has been extensively studied, especially on living individuals. The current studies (Part I and Part II) were designed to compare the use and utility of the different GSR testing techniques in a medical examiner setting. In Part I, the hands of deceased persons who died from undisputed suicidal handgun wounds were tested for GSR by SEM-EDX over a 4-year period. A total of 116 cases were studied and analyzed for caliber of weapon, proximity of wound, and results of GSR testing, including spatial deposition upon the hands. It was found that in only 50% of cases with a known self-inflicted gunshot wound was SEM-EDX positive for at least 1 specific particle for GSR. In 18% of the cases there was a discernible pattern (spatial distribution) of the particles on the hand such that the manner in which the weapon was held could be determined. Since only 50% of cases where the person is known to have fired a weapon immediately prior to death were positive for GSR by SEM-EDX, this test should not be relied upon to determine whether a deceased individual has discharged a firearm. Furthermore, in only 18% of cases was a discernible pattern present indicating how the firearm was held. The low sensitivity, along with the low percentage of cases with a discernible pattern, limits the usefulness of GSR test results by SEM-EDX in differentiating self-inflicted from non-self-inflicted wounds.     

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.     

Prevalence of organic gunshot residues in police vehicles

The present study investigated the organic gunshot residue (OGSR) background level of police vehicles in Switzerland. Specimens from 64 vehicles belonging to two regional police services were collected and analysed by LC-MS in positive mode. The driver’s and back seats were sampled separately to monitor potential differences between locations and to assess the risks of a suspect being contaminated by OGSR during transportation to a police station.The results showed that most of the 64 vehicles were uncontaminated (44 driver’s seats and 38 back seats respectively). Up to six of the seven targeted compounds were detected in a single sample, once on a driver’s seat and twice on back seats. The contamination frequency generally decreased as the number of compounds detected together increased. The amounts detected were in the low ng range and less than amounts generally detected just after discharge on a shooter. Our data indicated that detecting a combination of four or more compounds on a police vehicle seat appears to be a relatively rare occurrence. The background contamination observed was most probably due to secondary transfer from police officers (e.g. through recent participation in a shooting session or firearm manipulation) or from firearms stored in the vehicles. The present results might be used as a recommendation to minimize contact of a suspect with contaminated surfaces if OGSR is implemented in routine work in parallel to IGSR analysis.