Rapid Quantitative Analysis of Multiple Explosive Compound Classes on a Single Instrument via Flow-Injection Analysis Tandem Mass Spectrometry.

A flow-injection analysis tandem mass spectrometry (FIA MSMS) method was developed for rapid quantitative analysis of 10 different inorganic and organic explosives. Performance is optimized by tailoring the ionization method (APCI/ESI), de-clustering potentials, and collision energies for each specific analyte. In doing so, a single instrument can be used to detect urea nitrate, potassium chlorate, 2,4,6-trinitrotoluene, 2,4,6-trinitrophenylmethylnitramine, triacetone triperoxide, hexamethylene triperoxide diamine, pentaerythritol tetranitrate, 1,3,5-trinitroperhydro-1,3,5-triazine, nitroglycerin, and octohy-dro-1,3,5,7-tetranitro-1,3,5,7-tetrazocine with sensitivities all in the picogram per milliliter range. In conclusion, FIA APCI/ESI MSMS is a fast (<1 min/sample), sensitive (~pg/mL LOQ), and precise (intraday RSD < 10%) method for trace explosive detection that can play an important role in criminal and attributional forensics, counterterrorism, and environmental protection areas, and has the potential to augment or replace several of the existing explosive detection methods.

Use of Mass Spectrometric Vapor Analysis To Improve Canine Explosive Detection Efficiency.

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.

Characterization of nitrated sugar alcohols by atmospheric-pressure chemical-ionization mass spectrometry.

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 CH2 NO2 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. Copyright © 2016 John Wiley & Sons, Ltd.

Reagent approaches for improved detection of chlorate and perchlorate salts via thermal desorption and ionization.

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.

Vapor Pressure of Hexamethylene Triperoxide Diamine (HMTD) Estimated Using Secondary Electrospray Ionization Mass Spectrometry.

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.

Reagent assessment for detection of ammonium ion-molecule complexes.

RATIONALE: Ammonia (NH3) is an important chemical target in sensor applications such as trace explosives detection of ammonium nitrate (NH4NO3) and environmental monitoring. Ion-molecule reagent chemistries show potential to increase sensitivity in detection systems relying on atmospheric pressure ionization (API) of reagent-ammonium (M + NH4(+)) complexes. Gas-phase reagent selection assessment is based on mass spectrometric (MS) determination of binding constants relative to competitive ions and critical energies for ion-molecule complex dissociation. METHODS: Eight ammonium complexation reagents were identified and gas-phase ion-molecule interactions were studied using electrospray ionization. Binding constants were determined, in Log(K), using the competition method for one host molecule with three guests (NH4(+), Na(+), and K(+)) in single quadrupole MS. Critical energy determination was based on calibration of threshold activation voltage using collision-induced dissociation (CID) tandem mass spectrometry (MS/MS). RESULTS: This assessment informs selective binding affinity and intrinsic ion-molecule critical energy for dissociation. Relative NH4(+) binding affinity was highest for sucrose and 4-tert-butylcalix[6]arene, while 4-tert-butylcalix[6]arene and methyl acetoacetate showed the highest preferential binding of NH4(+) versus Na(+) and K(+). The intrinsic critical energy for NH4(+) binding was highest for crown ethers, tetraglyme and methyl acetoacetate. CONCLUSIONS: An MS-based framework was developed to quantitatively assess API ion-molecule reagent chemistries based on ammonium selectivity versus competing ions, and intrinsic ammonium binding strength and complex survivability for detection. Methyl acetoacetate is an attractive ammonium reagent for vapor-phase API techniques given its high vapor pressure, preferential selectivity, and high critical energy for dissociation.

Fate dynamics of environmentally exposed explosive traces.

The chemical and physical fates of trace amounts (<50 µg) of explosives containing 2,4,6-trinitrotoluene (TNT), hexahydro-1,3,5-trinitro-1,3,5-triazine (RDX), and pentaerythritol tetranitrate (PETN) were determined for the purpose of informing the capabilities of tactical trace explosive detection systems. From these measurements, it was found that the mass decreases and the chemical composition changes on a time scale of hours, with the loss mechanism due to a combination of sublimation and photodegradation. The rates for these processes were dependent on the explosive composition, as well as on both the ambient temperature and the size distribution of the explosive particulates. From these results, a persistence model was developed and applied to model the time dependence of both the mass and areal coverage of the fingerprints, resulting in a predictive capability for determining fingerprint fate. Chemical analysis confirmed that sublimation rates for TNT were depressed by UV (330-400 nm) exposure due to photochemically driven increases in the molecular weight, whereas the opposite was observed for RDX. No changes were observed for PETN upon exposure to UV radiation, and this was attributed to its low UV absorbance.