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.     

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 quantitative comparison of smokeless measurements

Measurements of the type and concentration of propellant and stabilizer additives in smokeless gunpowder are used by forensic scientists investigating the source of explosives and by military laboratories assuring the safety and efficacy of munitions. The National Institute of Standards and Technology recently assessed the state-of-the-practice of smokeless powder measurements through an international measurement comparison exercise. We here present results provided by the five participants (of 20 total) reporting quantitative as well as qualitative values for two handgun reloading powders. All five of these participants reported values for nitroglycerin (NG), ethyl centralite (EC), diphenylamine (DPA), and N-nitrosodiphenylamine (NnDPA). Several participants additionally reported the concentrations of secondary stabilizer decomposition products. The unstable NG propellant additive appears to be more susceptible to method-specific calibration biases then are the stabilizer additives. All results from one participant were strongly biased relative to those of the other four. The within-participant measurement uncertainties for all analytes were self-reported to be 1 to 5% relative; among the four concordant participants, the measurement ranges are 5 to 10% relative. There was little consistency among the participants as to what components of measurement variance were included in their uncertainty statements. A discussion of the certainties in these measurements and factors that affect the accuracy of gunpowder additive determinations is presented.     

Vacuum collection of gunpowder residues from clothing worn by shooting suspects, and their analysis by GC/TEA, IMS, and GC/MS

Experiments were conducted to collect gunpowder (propellant) residues from shooters' clothing by vacuum and to analyze them by gas chromatography/thermal energy analyzer (GC/TEA), ion mobility spectrometry (IMS), and gas chromatography/mass spectrometry (GC/MS). The residues were collected on fiberglass and Teflon filters using the portable vacuum sampler, all supplied with the IMS instrument. Several solvents were examined for the extraction of the propellant components from the filters. The extracts were centrifuged and/or filtered, concentrated by evaporation, and analyzed without any additional clean-up procedure. Based on the results of the study, an operational method for analysis of gunpowder residues was introduced into casework without changing the present operational technique for gunshot (primer) residue (GSR) analysis on clothing implemented by the Israel Police. In the modified method, the clothing is first sampled by double-side adhesive-coated aluminum stubs (the tape-lift method) for GSR analysis (the existing method), followed by vacuum collection for propellant residue examination. The issue of interpretation of the analytical results is discussed.     

Developing a quantitative extraction technique for determining the organic additives in smokeless handgun powder.

Compositional analysis of the organic additives in smokeless handgun powder can provide forensic information to associate known and questioned samples. A reliable method for the quantitative extraction of smokeless powder additives would strengthen these measurements. To achieve quantitative recovery, both supercritical fluid extraction (SFE) and ultrasonic solvent extraction (USE) were evaluated as candidate techniques. Following a detailed evaluation of the solvent choice, the recovery of spiked additive compounds, and the effect of the powder matrix, a reliable USE technique was developed. When quantitative USE recovery of the target analytes, nitroglycerin (NG), diphenylamine (DPA), and ethyl centralite (EC), is coupled with additive measurement by micellar capillary electrophoresis (CE), compositional information can be obtained in less than 1 h.     

Characterization of gunpowder samples using time-of-flight secondary ion mass spectrometry (TOF-SIMS)

Time-of-flight secondary ion mass spectrometry (TOF-SIMS) was utilized to obtain characteristic mass spectra from three different smokeless powders and six different black powder samples. In these mass spectra, peaks indicative of both the organic and inorganic additive constituents in the gunpowders were observed. TOF-SIMS was able to successfully differentiate between the different black and smokeless gunpowder samples analyzed with the aid of principal components analysis (PCA), a multivariate statistical analysis approach often used to reduce the dimensionality of complex data. TOF-SIMS was also used to obtain information about the spatial distribution of the various additives contained within the gunpowder samples. SIMS imaging demonstrated that that the samples could potentially be characterized by their 2-D structure, which varied from sample to sample. These results clearly demonstrate the feasibility of utilizing TOF-SIMS as a tool for the characterization and differentiation of gunpowder samples for general forensic applications.     

Mobile phase influence on electrospray ionization for the analysis of smokeless powders by gradient reversed phase high-performance liquid chromatography-ESIMS

The solution parameters associated with gradient elution reversed phase high-performance liquid chromatography (HPLC) were characterized by evaluating the electrospray ionization mass spectrometry (ESIMS) response of selected smokeless powder additives. Using direct liquid infusion, the positive ion ESIMS responses were determined for three general classes of powder constituents: dialkylphthalate acid esters, N,N'-dialkyl-N,N'-diphenyl urea based stabilizers and nitroso-, nitro-, and dinitro- derivatives of diphenylamine. The relative ESIMS intensities of the powder components were investigated as a function of three solution parameters: ammonium acetate concentration, pH, and percent methanol. The effect of the ammonium acetate concentration demonstrates that the electrolyte is required for efficient ionization and the ESIMS intensity was optimal at a concentration of 2mM for the selected compounds, except 2,4'-dinitrodiphenylamine. The aqueous solution pH, corresponding to the available protons in solution, did not have a significant effect on the ESIMS intensity of the analytes. The percent methanol was evaluated with both decreasing and constant electrolyte concentrations to demonstrate the effects of droplet stability and ion transfer into the gas phase. These findings were applied to the analysis of the selected smokeless powder additives using HPLC-ESIMS to illustrate increased sensitivity for the protonated molecules.     

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.     

A qualitative comparison of smokeless powder measurements

In the spring of 2000, the National Institute of Standards and Technology and nineteen participants conducted a comparison of smokeless powder additive compositional measurements. The purpose of this exercise was to determine the state-of-the-practice for forensic smokeless powder determinations. For the comparison, two handgun reloading powder samples were mixed and were compositionally evaluated for homogeneity by NIST. Participant laboratories included military, academic, and state/local, federal, and international forensic agencies. We solicited qualitative data identifying nitroglycerin, diphenylamine, N-nitrosodiphenylamine, and ethyl centralite. In addition, some laboratories provided identification of additional ingredients, such as nitrocellulose, or reported other measurements, such as dimensional morphology. In this paper, laboratory identification of the smokeless powder additives and a summary of the measurement methods used for the evaluations are presented. All laboratories correctly identified NG and the major stabilizers. Some disparity between laboratories was noted for the identification of minor (<0.01% by weight) stabilizers and stabilizer decomposition products.     

A novel method for extraction and analysis of gunpowder residues on double-side adhesive coated stubs

A study was conducted to develop an efficient method for extraction and analysis of gunpowder (propellant) residues from double-side adhesive coated stubs, which are used for sampling suspects or their clothing for gunshot (primer) residues (GSR). Conductive and non-conductive double-side adhesives were examined, and the analysis was carried out by gas chromatography/thermal energy analyzer (GC/TEA) and ion mobility spectrometry (IMS). The optimal procedure for the extraction, as was developed in the present study, employs two stages: (1) extraction of the stubs with a mixture of 80% v/v aqueous solution of 0.1% w/v of sodium azide and 20% v/v of ethanol employing sonication at 80 degrees C for 15 min. and (2) residues from the obtained extract were further extracted with methylene chloride. The methylene chloride phase was concentrated by evaporation prior to analysis. Extraction efficiencies of 30-90% for nitroglycerine (NG) and for 2,4-dinitro toluene (2,4-DNT) were found. No significant interferences in the analysis were observed from the adhesives or skin. Interferences were observed in the analysis by the GC/TEA of the samples collected from hair. The method enables analysis of propellant residues on a double-side adhesive coated stub after it was examined for primer residues by scanning electron microscopy/energy dispersive X-ray spectroscopy (SEM/EDX). Thus, the probative value of the evidence may be increased.     

Detection of explosives in hair using ion mobility spectrometry

Conventional explosives 2,4,6-trinitrotoluene (TNT), nitroglycerin (NG), and ethylene glycol dinitrate (EGDN) sorbed to hair can be directly detected by an ion mobility spectrometer (IMS) in E-mode (for explosives). Terrorist explosive, triacetone triperoxide (TATP), difficult to detect by IMS in E-mode, was detected in N-mode (for narcotics). Three modes of sample introduction to IMS vapor desorption unit were used: (i) placement of hair directly into the unit, (ii) swabbing of hair and placement of swabs (i.e., paper GE-IMS sample traps) into the unit, and (iii) acetonitrile extracts of hair positioned on sample traps and placed into the unit. TNT, NG, and EGDN were detected in E-mode by all three sample introduction methods. TATP could only be detected by the acetonitrile extraction method after exposure of the hair to vapor for 16 days because of lower sensitivity. With standard solutions, TATP detection in E-mode required about 10 times as much sample as EGDN (3.9 mug compared with 0.3 mug). IMS in N-mode detected TATP from hair by all three modes of sample introduction.     

Validation of an ion mobility spectrometry (IMS) method for the detection of heroin and cocaine on incriminated material

The validation of a qualitative ion mobility spectrometry (IMS) procedure for the detection of trace amounts of heroin and cocaine on incriminated material using a vacuum cleaner for sampling is presented. The limit of detection, the limit of decision, selectivity and robustness were determined. As an approach, robustness was determined using ionizational interferences and matrix effects. By using this simple sampling procedure, a positive result for incriminated clothes needs a contamination of 250ng cocaine and 1000ng heroin, respectively.     

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.     

A comparison of smokeless powders and mixtures by capillary zone electrophoresis

The analysis of inorganic ions present in smokeless and muzzleloading powders has been performed using capillary zone electrophoresis (CZE). Previous publications have examined inorganic low explosives using CZE, but have not looked at the ion profiles from smokeless powders. In this report, seven commercially available smokeless powders were analyzed as unburned powder and burned residue. The results demonstrate that ionic profiles can be used to characterize smokeless powders. Our analysis also included a smokeless powder/ Pyrodex combination to determine if smokeless powder ions are distinguishable in a mixture; however, the high concentration of ions present in Pyrodex RS prevented its detection. In addition, five different smokeless powder samples as well as Pyrodex RS were collected for analysis subsequent to deflagration in fifteen plastic pipe bombs. The relative ion concentrations between these powders can be used to illustrate the differences between open burning and pipe bomb deflagration.     

Particle characteristics of trace high explosives: RDX and PETN

The sizes of explosives particles in fingerprint residues produced from C-4 and Semtex-1A were investigated with respect to a fragmentation model. Particles produced by crushing crystals of RDX and PETN were sized by using scanning electron microscopy, combined with image analysis, and polarized light microscopy was used for imaging and identifying explosive particles in fingerprint residues. Crystals of RDX and PETN fragment in a manner that concentrates mass in the largest particles of the population, which is common for a fragmentation process. Based on the fingerprints studied, the particle size to target for improving mass detection in fingerprint residues by ion mobility spectrometry (IMS) is > or = 10 microm in diameter. Although particles smaller than 10 microm in diameter have a higher frequency, they constitute < 20% of the total mass. Efforts to improve collection efficiency of explosives particles for detection by IMS, or other techniques, must take into consideration that the mass may be concentrated in a relatively few particles that may not be homogeneously distributed over the fingerprint area. These results are based on plastic-bonded explosives such as C-4 that contain relatively large crystals of explosive, where fragmentation is the main process leading to the presence of particles in the fingerprint residues.     

Characterization of the explosive triacetone triperoxide and detection by ion mobility spectrometry

The improvised explosive triacetone triperoxide (TATP) was synthesized and characterized by 1H-nuclear magnetic resonance (NMR), 13C-NMR, Raman and infrared (IR) spectroscopy. Triacetone triperoxide was subsequently analyzed by ion mobility spectrometry (IMS) in positive ion mode, and detected as a cluster of three peaks with a drift time of the most intense peak at 13.06 ms. Triacetone triperoxide was then analyzed after dissolution in toluene, where a dramatic increase in peak intensity was observed, at a flight time of 12.56 ms (K0=2.71 cm2V(-1)s(-1)). Triacetone triperoxide was subsequently analyzed by coupling the ion mobility spectrometer to a triple quadrupole mass spectrometer, where a single peak at m/z of 223 atomic mass units identified the species present in the ion mobility spectra as being triacetone triperoxide.     

Using Gas Chromatography with Ion Mobility Spectrometry to Resolve Explosive Compounds in the Presence of Interferents*

Abstract: Ion mobility spectrometry (IMS) is a valued field detection technology because of its speed and high sensitivity, but IMS cannot easily resolve analytes of interest within mixtures. Coupling gas chromatography (GC) to IMS adds a separation capability to resolve complex matrices. A GC‐IONSCAN^® operated in IMS and GC/IMS modes was evaluated with combinations of five explosives and four interferents. In 100 explosive/interferent combinations, IMS yielded 21 false positives while GC/IMS substantially reduced the occurrence of false positives to one. In addition, the results indicate that through redesign or modification of the preconcentrator there would be significant advantages to using GC/IMS, such as enhancement of the linear dynamic range (LDR) in some situations. By balancing sensitivity with LDR, GC/IMS could prove to be a very advantageous tool when addressing real world complex mixture situations.     

Associating gunpowder and residues from commercial ammunition using compositional analysis

Qualitatively identifying and quantitatively determining the additives in smokeless gunpowder to calculate a numerical propellant to stabilizer (P/S) ratio is a new approach to associate handgun-fired organic gunshot residues (OGSR) with unfired powder. In past work, the P/S values of handgun OGSR and cartridges loaded with known gunpowders were evaluated. In this study, gunpowder and residue samples were obtained from seven boxes of commercial 38 caliber ammunition with the goals of associating cartridges within a box and matching residues to unfired powders, based on the P/S value and the qualitative identity of the additives. Gunpowder samples from four of the seven boxes of ammunition could be easily differentiated. When visual comparisons of the cartridge powders were considered in addition to composition, powder samples from all seven boxes of ammunition could be reliably differentiated. Handgun OGSR was also collected and evaluated in bulk as well as for individual particles. In some cases, residues could be reliably differentiated based on P/S and additive identity. It was instructive to evaluate the composition of individual unfired gunpowder and OGSR particles. We determined that both the numerical centroid and dispersity of the P/S measurements provide information for associations and exclusions. Associating measurements from residue particles with those of residue samples collected from a test firing of the same weapon and ammunition appears to be a useful approach to account for any changes in composition that occur during the firing process.     

Ion mobility spectrometry of drugs of abuse in customs scenarios: concentration and temperature study.

A custom-built ion mobility spectrometer has been used to obtain the IMS spectra of cocaine, heroin, amphetamine sulfate and LSD at different drug concentrations and desorption temperatures. Practical detection limits for these four drugs were obtained as a function of desorber temperature and for heroin as a function of analysis time. Spectral and ionization interferences for each of the four drugs of interest were determined. Spectral interferences by innocuous materials are few; ionization interferences occur only at very high ratios of the mass of innocuous material to that of the drug of interest.