Publications

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.

RATIONALE: The nitrated sugar alcohols mannitol hexanitrate (MHN), sorbitol hexanitrate (SHN) and xylitol pentanitrate (XPN) are in the same class of compounds as the powerful military-grade explosive pentaerythritol tetranitrate (PETN) and the homemade explosive erythritol tetranitrate (ETN) but, unlike for PETN and ETN, ways to detect MHN, SHN and XPN by mass spectrometry (MS) have not been fully investigated. METHODS: Atmospheric-pressure chemical-ionization mass spectrometry (APCI-MS) was used to detect ions characteristic of nitrated sugar alcohols. APCI time-of-flight mass spectrometry (APCI-TOF MS) and collision-induced dissociation tandem mass spectrometry (CID MS/MS) were used for confirmation of each ion assignment. In addition, the use of the chemical ionization reagent dichloromethane was investigated to improve sensitivity and selectivity for detection of MHN, SHN and XPN. RESULTS: All the nitrated sugar alcohols studied followed similar fragmentation pathways in the APCI source. MHN, SHN and XPN were detectable as fragment ions formed by the loss of NO2, HNO2, NO3, and CH2NO2 groups, and in the presence of dichloromethane chlorinated adduct ions were observed. It was determined that in MS/MS mode, chlorinated adducts of MHN and SHN had the lowest limits of detection (LODs), while for XPN the lowest LOD was for the [XPN-NO2]- fragment ion. Partially nitrated analogs of each of the three compounds were also present in the starting materials, and ions attributable to these compounds versus those formed from in-source fragmentation of MHN, SHN, and XPN were distinguished and assigned using liquid chromatography APCI-MS and ESI-MS. CONCLUSIONS: The APCI-MS technique provides a selective and sensitive method for the detection of nitrated sugar alcohols. The methods disclosed here will benefit the area of explosives trace detection for counterterrorism and forensics.

RATIONALE: Techniques for improving the detectability of chlorate and perchlorate salts with thermal desorption based ionizers (i.e. radioactive, corona discharge and photoionization-based) are desired. This work employs acidic reagents to chemically transform chlorate and perchlorate anions into traces of chloric and perchloric acid. These high vapor pressure acids are easier to detect than the originating salts. METHODS: The efficacy of the reagent chemistry was quantified with a triple-quadrupole mass spectrometer interfaced with a custom-built thermal-desorption atmospheric-pressure chemical ionization (TD-APCI) source. Additional experiments were conducted using tandem IMS/MS instrumentation. Reagent pKa and pH values were varied in order to gain a better understanding of how those parameters affect the degree of observed signal enhancement. RESULTS: Samples of chlorates and perchlorates treated with liquid acidic reagents exhibit signal enhancement of up to six orders of magnitude compared with signals from untreated analytes. Three orders of magnitude of signal enhancement are demonstrated using solid-state reagents, such as weakly acidic salts and polymeric acids. Data is presented that demonstrates the compatibility of the solid-state approach with both MS and IMS/MS platforms. CONCLUSIONS: Several methods of acidification were demonstrated for enhanced vaporization and detection of chlorates and perchlorates. For applications where rapid surface collection and analysis for chlorates and perchlorates are desired, the solid-state approaches offer the simplest means to integrate the reagent chemistry into MS or IMS detection.