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.
United States military Composition C-4 explosive contains 91% cyclotrimethylene trinitramine (RDX), 5.3% dioctyl sebacate or adipate (DOS or DOA), 2.1% polyisobutylene (PIB), and 1.6% oil. The original military specification required low viscosity engine oil, but this has since been changed to a specially manufactured mineral oil, also called “process oil.” Differentiation of military and commercial Composition C-4 may be possible by analyzing the oil. In this study, samples of Composition C-4 were taken from various lots of U.S. military M112 demolition blocks from two commercially manufactured brands sold in the U.S. The oil and plasticizer were extracted with pentane, and the plasticizer was removed using silica solid phase extraction cartridges. The oil was then analyzed by high-temperature gas chromatography/mass spectrometry (HTGC/MS). Results indicated that HTGC/MS is an excellent discriminating technique for oil comparisons; however, differentiation of Composition C-4 is limited by manufacturer production and distribution practices.
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.
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.
The analysis of motor oils has wide applications in the forensic science field from comparing lubricants transferred between an automobile and a victim or crime scene to differentiating the compositions of plastic explosives. In this study, 40 unused motor oils were analyzed and compared by high-temperature gas chromatography-mass spectrometry to determine the potential for oil individualization. Oil samples were also collected from the crankcase dipsticks of 30 cars. Twenty-six of these oils could be differentiated from each other based on visual comparisons of the unresolved envelope (baseline rise due to incomplete separation) and the resolved hydrocarbons in the raw total ion chromatograms (TICs) and smoothed TIC data. Four of these oils were analyzed as unknowns and were correctly related to the corresponding vehicle. The use of extracted ion profiles (EIPs) was explored as a means to further discriminate between the indistinct samples based on the polycyclic aromatic hydrocarbon (PAH) content. The research discussed in this paper demonstrated that differentiation of motor oils was possible by examining the TIC, smoothed TIC, and EIP data.
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