Lauryn E. DeGreeff

Technical note: Headspace analysis of explosive compounds using a novel sampling chamber

The development of instruments and methods for explosive vapor detection is a continually evolving field of interest. A thorough understanding of the characteristic vapor signatures of explosive material is imperative for the development and testing of new and current detectors. In this research a headspace sampling chamber was designed to contain explosive materials for the controlled, reproducible sampling and characterization of vapors associated with these materials. In a detonation test, the chamber was shown to contain an explosion equivalent to three grams of trinitrotoluene (TNT) without damage to the chamber. The efficacy of the chamber in controlled headspace sampling was evaluated in laboratory tests with bulk explosive materials. Small quantities of TNT, triacetone triperoxide (TATP) and hexamethylene triperoxide diamine (HMTD) were separately placed in the sampling chamber, and the headspace of each material was analyzed by gas chromatography/mass spectrometry (GC/MS) with online cryogenic trapping to yield characteristic vapor signatures for each explosive compound. Chamber sampling conditions, temperature and sampling time, were varied to demonstrate suitability for precise headspace analysis.

Factors affecting the intramolecular decomposition of hexamethylene triperoxide diamine and implications for detection.

Hexamethylene triperoxide diamine (HMTD) is an easily synthesized and highly sensitive organic peroxide frequently used as a primary explosive. The vapor pressure of HMTD is very low, impeding vapor detection, especially when compared to other peroxide explosives, such as triacetone triperoxide (TATP) or diacetone diperoxide (DADP). Despite this fact, HMTD has a perceptible odor that could be utilized in the indirect detection of HMTD vapor. Headspace measurements above solid HMTD samples confirm that HMTD readily decomposes under ambient conditions to form highly volatile products that include formic acid, ammonia, trimethylamine and formamides. The presence and quantity of these compounds are affected by storage condition, time, and synthetic method, with synthetic method having the most significant effect on the content of the headspace. A kinetic study of HMTD decomposition in solution indicated a correlation between degradation rate and the presence of decomposition species identified in the headspace, and provided further insight into the mechanism of decomposition. The study provided evidence for a proton assisted decomposition reaction with water, as well as an intramolecular decomposition process facilitated by the presence of water.

Quantitative analysis of vaporous ammonia by online derivatization with gas chromatography ‐ mass spectrometry with applications to ammonium nitrate-based explosives

A novel method for the detection of vaporous products was developed utilizing a derivatizing agent collected onto a cryo-cooled gas chromatograph (GC) inlet, with analysis by gas chromatography-mass spectrometry (GC-MS). The technique was applied to the detection of ammonia, which has been difficult to detect at trace levels, particularly in the presence of other chemical interferents, due to its small mass and high volatility. To address this, the ammonia is derivatized in the inlet with butyl chloroformate to produce butyl carbamate, a compound that is retained by GC columns and compatible with standard GC-MS analysis. This method was then used to quantify the ammonia headspace vapor concentration produced from the dissociation of bulk ammonium nitrate as well as from mixtures with aluminum and petroleum jelly, which are fuels commonly used in homemade explosives (HMEs).

Mixed Vapor Generation Device for delivery of homemade explosives vapor plumes

While there is a large body of research on the properties and detection of traditional military high explosives and propellant low explosives, there is a dearth of research on homemade explosive (HME) materials, though they are prevalent today. The safety of working with these materials in the laboratory is the greatest limiting factor preventing HME research. A vapor delivery tool, the Mixed Vapor Generation Device (MV-Gen), was designed to safely contain the individual solid or liquid components that often compose homemade explosives vapor plumes and deliver the mixed component vapors for instrumental sampling and analysis. Within the MV-Gen, each component is separated and only the vapors mix as they are carried through the device by flowing air. The resulting mixed vapor is representative of either mixed explosive material or bulk explosives. Component materials are held in up to four individual, removable vials with vapor concentrations controlled by vial orifice size, temperature, and diluent airflow. The total concentration can be adjusted by altering vial temperature via a thermal water jacket surrounding the entirety of the device, or by adjusting the flow rate of diluent air through the device. The MV-Gen was evaluated first with surrogate compounds, followed by two types of homemade explosives, to include a binary explosive mixture and a peroxide explosive. To evaluate the device, vapors were cold-trapped on an online sampling system and analyzed by gas chromatography/mass spectrometry. It was determined that the device yielded reproducible vapor concentrations of both single and mixed components, and the ratio of these vapors can be easily adjusted to mimic varying forms of homemade explosives.

Considerations in the vapor analysis of traditional vs. homemade explosives

Vapor detection of explosives is important for non-contact detection, vaporization of collected particles, and canine detection efforts. Much research has been carried out to aid in the vapor detection of traditional explosives, such as the nitro-based explosives like trinitrotoluene (TNT) and black and smokeless powders. Many of these explosives have extremely low vapor pressures, thus related vaporous components of the vapor signature are used for detection by proxy. As most of these explosives are extremely stable, their vapor signatures do not change significantly with time or environment. In contrast, comparatively little research has been done on the vapor detection of homemade explosives (HMEs), whose unique chemistries make vapor signature analysis a more complex problem. In this work, the vapor signatures of two types of HMEs were explored across time and environmental conditions, including ammonium nitrate-based binary explosives and organic peroxide explosive.

A novel odor delivery device for homemade explosive analysis

A novel odor delivery device was designed to safely contain the solid or liquid components of homemade explosives (HMEs) and deliver the HME odor signature for passive or active sampling. Within the device, odors from the separately-housed components mix as they move through the device towards the outlet. The resulting mixed odor is representative of that which would be achieved from the actual mixed explosive material. For active sampling, air flows from an external source, through the device, carrying the mixed analyte odor towards the instrument of choice. For passive sampling, component odor diffuses from the bulk material through a Teflon neck, where odors mix before exiting the device at a bowl-shaped outlet. Both active and passive transport devices have been tested with surrogate components as well as actual explosive components and have been shown to deliver the mixed odor of separated components.