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.

Improvised explosive devices (IEDs) are charged devices often used by terrorists and criminals to create public panic. When the general public is targeted by an act of terrorism, people who are not injured or killed in the explosion remain in fear until the perpetrator(s) has been apprehended. Methods that can provide investigators and first responders with prompt investigative information are required in such cases. However, information is generally not provided quickly, in part because of time-consuming techniques employed in many forensic laboratories. As a result, case report turnaround time is longer. Direct analysis in real time - mass spectrometry (DART-MS) is a promising analytical technique that can address this challenge in the Forensic Science community by permitting rapid trace analysis of energetic materials. The builder of an IED will often charge the device with materials that are readily available. The most common materials employed in the construction of IEDs are black and smokeless powder. However, other materials may include ammonia- or peroxide-based materials such as common household detergents. Smokeless powder is a propellant that is readily available to civilians. They are typically used for reloading ammunition and are sold in large quantities each year in the United States. Some states have stricter regulations than others but typically a firearms license is all that’s required to possess smokeless powder. Smokeless powder is considered a low explosive which is capable of causing an explosion if a sufficient quantity is deflagrated inside a confined container. The most commonly employed confirmatory techniques for the analysis of smokeless powder are gas chromatography-mass spectrometry (GC-MS) or liquid chromatography-mass spectrometry (LC-MS). These methods often require extensive and time-consuming sample preparation procedures to prepare the powders for analysis. In addition to lengthy sample preparation procedures, GC-MS and LC-MS often require chromatographic separations that can range anywhere from 5 to 30 minutes or longer per sample. Ion mobility spectrometry (IMS) is widely used for the field analysis of smokeless powder and can provide faster results in comparison to GC-MS or LC-MS. However, identification is limited to drift time and no structural information is provided unless coupled to a mass spectrometer. In an effort to accelerate the speed of collection and characterization of smokeless powder, an analytical approach that utilizes novel wire mesh coated with CarbopackTM X, dynamic headspace concentration and DART-MS was evaluated to determine if the approach could generate information rich chemical attribute signatures (CAS) for smokeless powder. CarbopackTM X is a graphitized carbon material that has been employed for the collection of various volatile and semi-volatile organic compounds. The goal of using CarbopackTM X coated wire mesh was to increase the collection efficiency of smokeless powder in comparison to traditional swabbing and swiping methods. DART is an ambient ionization technique that permits analysis of a variety of samples in seconds with minimal to no sample preparation and offers several advantages over conventional methods. Heating time, heating temperature and flow rate for dynamic headspace concentration were optimized using Hodgdon Lil’ Gun smokeless powder. DART-MS was compared to GC-MS and validated using the National Institute of Standards and Technology reference material 8107 (NIST RM 8107) smokeless powder standard. Additives and energetic materials from unburnt and burnt smokeless powders were rapidly and efficiently captured by the CarbopackTM X coated wire mesh and successfully detected and identified using DART-MS. The DART source temperature was evaluated with the goal of providing the most efficient desorption of the analytes adsorbed onto the wire mesh. For this to be a robust approach in forensic analysis, chemometric analysis employing predictive models was used to simplify the data and increase the confidence of assigning a mass spectrum to a particular powder. Predictive models were constructed using the machine learning techniques available in Analyze IQ Lab and evaluated for their performance in classifying three smokeless powders: Alliant Reloder 19, Hodgdon LEVERevolution and Winchester Ball 296. The models were able to accurately predict the presence or absence of these three powders from burnt residues with error rates that were less than 4%. This approach has demonstrated the capability of generating comparable data and sensitivity in a significantly shorter amount of time in comparison to GC-MS. In addition, DART-MS also permits the detection of targeted analytes that are not amenable to GC-MS. The speed and efficiency associated with both the sample preparation technique and DART-MS, and the ability to employ chemometric analysis to the generated data demonstrate an attractive and viable alternative to conventional techniques for smokeless powder analysis.