A rapid method for vapor pressure measurement was developed and used to derive the vapor pressure curve of the thermally labile peroxide-based explosive hexamethylene triperoxide diamine (HMTD) over the temperature range from 28 to 80 °C. This method uses a controlled flow of vapor from a solid-phase HMTD source that is presented to an ambient-pressure-ionization mass spectrometer equipped with a secondary-electrospray-ionization (SESI) source. The subpart-per-trillion sensitivity of this system enables direct detection of HMTD vapor through an intact [M + H](+) ion in real time at temperatures near 20 °C. By calibrating this method using vapor sources of cocaine and heroin, which have known pressure-temperature (P-T) curves, the temperature dependence of HMTD vapor was determined, and a Clausius-Clapeyron plot of ln[P (Pa)] vs 1/[T (K)] yielded a straight line with the expression ln[P (Pa)] = {(-11091 ± 356) × 1/[T (K)]} + 25 ± 1 (error limits are the standard error of the regression analysis). From this equation, the sublimation enthalpy of HMTD was estimated to be 92 ± 3 kJ/mol, which compares well with the theoretical estimate of 95 kJ/mol, and the vapor pressure at 20 °C was estimated to be ∼60 parts per trillion by volume, which is within a factor of 2 of previous theoretical estimates. Thus, this method provides not only the first direct experimental determination of HMTD vapor pressure but also a rapid, near-real-time capability to quantitatively measure low-vapor-pressure compounds, which will be useful for aiding in the development of training aids for bomb-sniffing canines.

Unlike current chemical trace detection technology, dogs actively sniff to acquire an odor sample. Flow visualization experiments with an anatomically-similar 3D printed dog’s nose revealed the external aerodynamics during canine sniffing, where ventral-laterally expired air jets entrain odorant-laden air toward the nose, thereby extending the “aerodynamic reach” for inspiration of otherwise inaccessible odors. Chemical sampling and detection experiments quantified two modes of operation with the artificial nose-active sniffing and continuous inspiration-and demonstrated an increase in odorant detection by a factor of up to 18 for active sniffing. A 16-fold improvement in detection was demonstrated with a commercially-available explosives detector by applying this bio-inspired design principle and making the device “sniff” like a dog. These lessons learned from the dog may benefit the next-generation of vapor samplers for explosives, narcotics, pathogens, or even cancer, and could inform future bio-inspired designs for optimized sampling of odor plumes.

Canines remain the gold standard for explosives detection in many situations, and there is an ongoing desire for them to perform at the highest level. This goal requires canine training to be approached similarly to scientific sensor design. Developing a canine training regimen is made challenging by a lack of understanding of the canine's odor environment, which is dynamic and typically contains multiple odorants. Existing methodology assumes that the handler's intention is an adequate surrogate for actual knowledge of the odors cuing the canine, but canines are easily exposed to unintentional explosive odors through training material cross-contamination. A sensitive, real-time (∼1 s) vapor analysis mass spectrometer was developed to provide tools, techniques, and knowledge to better understand, train, and utilize canines. The instrument has a detection library of nine explosives and explosive-related materials consisting of 2,4-dinitrotoluene (2,4-DNT), 2,6-dinitrotoluene (2,6-DNT), 2,4,6-trinitrotoluene (TNT), nitroglycerin (NG), 1,3,5-trinitroperhydro-1,3,5-triazine (RDX), pentaerythritol tetranitrate (PETN), triacetone triperoxide (TATP), hexamethylene triperoxide diamine (HMTD), and cyclohexanone, with detection limits in the parts-per-trillion to parts-per-quadrillion range by volume. The instrument can illustrate aspects of vapor plume dynamics, such as detecting plume filaments at a distance. The instrument was deployed to support canine training in the field, detecting cross-contamination among training materials, and developing an evaluation method based on the odor environment. Support for training material production and handling was provided by studying the dynamic headspace of a nonexplosive HMTD training aid that is in development. These results supported existing canine training and identified certain areas that may be improved.