Indiana University-Purdue University Indianapolis (IUPUI) / Analysis of explosives (intact and post-blast) is of interest to the forensic science community to qualitatively identify the explosive(s) in an improvised explosive device (IED). This requires high sensitivity, selectivity, and specificity. Forensic science laboratories typically utilize visual/microscopic exams, spectroscopic analysis (e.g., Fourier Transform Infrared Spectroscopy (FTIR)) and gas chromatography/mass spectrometry (GC/MS) for explosive analysis/identification. However, GC/MS has limitations for explosive analysis due to difficulty differentiating between structural isomers (e.g., 2,4-dinitrotoluene, 2,5-dinitrotoluene and 2,6- dinitrotoluene) and thermally labile compounds (e.g., ethylene glycol dinitrate (EGDN), nitroglycerine (NG) and pentaerythritol tetranitrate (PETN)) due to mass spectra with very similar fragmentation patterns. The development of a benchtop vacuum ultraviolet spectrometer coupled to a gas chromatography (GC/VUV) was developed in 2014 with a wavelength region of 120 nm to 430 nm. GC/VUV can overcome limitations in differentiating explosive compounds that produces similar mass spectra. This work encompasses analysis of explosive compounds via GC/VUV to establish the sensitivity, selectivity, and specificity for the potential application for forensic explosive analysis. Nitrate ester and nitramine explosive compounds thermally decompose in the VUV flow cell resulting in higher specificity due to fine structure in the VUV spectra. These fine structures originate as vibronic and Rydberg transitions in the small decomposition compounds (nitric oxide, carbon monoxide, formaldehyde, water, and oxygen) and were analyzed computationally. The thermal decomposition process was further investigated for the determination of decomposition temperatures for the nitrate ester and nitramine compounds which range between 244 oC and 277 oC. Nitrated compounds were extensively investigated to understand the absorption characteristics of the nitro functional group in the VUV region. The nitro absorption maximum appeared over a wide range (170 - 270 nm) with the wavelength and intensity being highly dependent upon the structure of the rest of the molecule. Finally, the GC/VUV system was optimized for post-blast debris analysis. Parameters optimized include the final temperature of a ramped multimode inlet program (200 oC), GC carrier gas flow rate (1.9 mL/min), and VUV make-up gas pressure (0.00 psi). The transfer line/flow cell temperature was determined not to be statistically significant.

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Improvised explosive devices (IEDs) continue to be a national threat to the safety and security of the public. Research in explosives analysis for intact and post-blast samples continue to be a topic in which practitioners are constantly improving and searching for faster methods and techniques to analyze these sample types. The key role crime laboratories play in analyzing these sample types can have limitations, such as increasing turnaround times and backlogs. This concern additionally plays a role in the safety of the public if an unknown individual has not been discovered. Current analytical instrumentation in which explosives are analyzed includes Gas Chromatography – Mass Spectrometry (GC-MS), Liquid Chromatography – Mass Spectrometry (LC-MS), and Ion Mobility Spectrometry (IMS). Each instrument has benefits in the analytical results obtained. Direct Analysis in Real Time - Mass Spectrometry (DART-MS) has shown a significant promise as an analytical approach that can help remedy the time an explosive sample is analyzed, while additionally providing discriminating analytical results. Previous research has shown that DART-MS is capable of analyzing explosives, including smokeless powder. A limitation currently in the area of smokeless powder analysis with DART-MS is the application of utilizing this method and technology to realistic casework that may be encountered in forensic laboratories. Intact and post-blast explosive samples encountered in forensic laboratories arrive in various states and conditions. For example, the severity of the blast and environmental factors may play a role in the detection of smokeless powder on these sample types. To provide objective information and additional research, studies were conducted with mixture samples of smokeless powder and potential matrices that may be encountered in real world case samples. Faster processing time, in addition to the discrimination of smokeless powder, was the ultimate goal of this research. Due to the complexity of the mass spectra that may be generated from sample mixtures, an extraction technique coupled with DART-MS was investigated. A liquid-liquid extraction (LLE) method and dynamic headspace concentration using Carbopack™ X coated wire mesh were tested for the effectiveness of separating the analytes of interest of smokeless powder from various matrix interferences. Hodgdon Hornady LEVERevolution (HHL) smokeless powder, Pennzoil 10W-40 (P10W40) motor oil, and residue from metal end caps (China SLK brand) and black steel pipe nipples (Schedule 40) were used during the course of the matrix interference study. The method of applying dynamic headspace concentration using Carbopack™ X coated wire mesh and analysis by DART-MS provides an effective alternative to obtaining mass spectral data in a shorter amount of time, compared to techniques currently used in forensic laboratories. Effective separation was not achieved using the various LLE methods tested. Further testing would be required in order to evaluate the feasibility of implementing the technique as a sample preparation approach prior to analysis by DART-MS.

<p>  </p> <p>With bombings in the United States on the rise for the first time since 2016, the detection and identification of explosives remains of pertinent interest to law enforcement agencies. This work presents two soon-to-be published research articles that focus on the detection and identification of explosives by both chemical instrumentation and canines. The first article, <em>Quantitative Analysis of Smokeless Powder Particles in Post-Blast Debris via Gas Chromatography/Vacuum Ultraviolet Spectroscopy (GC/VUV)</em>, utilizes gas chromatography/vacuum ultraviolet spectroscopy (GC/VUV) to determine the difference in chemical composition of two smokeless powders in both pre- and post-blast conditions. The compounds of interest in this study were nitroglycerin, 2,4-dinitrotoluene, diphenylamine, ethyl centralite, and di-n-butyl phthalate. Concentration changes between pre- and post-blast smokeless powder particles were determined as well as microscopic differences between pre- and post-blast debris for both smokeless powders in all devices. To our knowledge, this is the first use of GC/VUV for the quantification of explosives. The second article, <em>An Odor-Permeable Membrane Device for the Storage of Canine Training Aids</em>, proposes the use of an odor-permeable membrane device (OPMD) as a standardized storage method for canine training aids. It is hypothesized that the OPMD would minimize cross-contamination between training aids, and that the OPMD could be used for canine training as well as storage. The goal of this research is to use flux and evaporation rate to quantify the explosive odor that escapes from the OPMD compared to unconfined explosives. Preliminary data suggests that there is an exponential relationship between relative boiling point and evaporation rate. It has been determined that compounds with higher boiling points have lower evaporation rates than compounds that have lower boiling points. The materials studied thus far are known odor compounds produced by explosive formulations. These include nitromethane, nitroethane, 1-nitropropane, r-limonene, and toluene. </p>