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.

The effect of standing acoustic waves on the formation of laser-induced air plasmas.

The expected location of an air plasma produced by a focused YAG laser pulse has been found to be influenced by the acoustics of the surrounding environment. In open air, the expected location of a laser-induced air plasma is centered close to the focal point of the lens focusing the laser beam. When confining the same beam coaxially along the interior of a quartz tube, the expected location of the air plasma shifts away from the focal point, toward the focusing lens, in a region of less laser fluence. This shift is caused by an interaction between standing acoustic waves (formed from sound waves produced by previous laser-induced plasmas) and the impinging laser pulse. Standing acoustic waves in a tube produce areas (antinodes) of slightly higher and slightly lower pressure than ambient atmospheric conditions, that in turn have a noticeable affect on the probability of creating an air plasma at a given location. This leads to two observed phenomena: Increased probability of air plasma formation before the optical focal point is reached, and the formation of distinct (separate) air plasmas at the antinodes themselves.

Utilization of the coherence function with Welch's method for signal analysis in low resolution laser-induced breakdown spectroscopy.

This work presents a technique by which a low resolution ( approximately 1 nm) fiberoptic spectrometer may be used to definitively identify elements and molecular fragments in laser-induced breakdown spectroscopy. Commercial laser-induced breakdown spectroscopy (LIBS) spectrometers have high resolution in the area of spectral interest, and software is used to identify elements via a look-up table containing known spectral lines. When analyzing spectra from a lower resolution fiber-optic spectrometer, software based on look-up tables can produce erroneous results, reporting elements absent from the sample. As a solution to this problem, an analysis using the coherence function in conjunction with Welch's method is used to compare sample spectra with a library of reference spectra, which contain peaks primarily from a single element. The analysis has proved to be adept at identifying specific elemental signatures in multi-component samples. The technique leverages the increased information content of concomitant atomic emission lines, which are easily collected with a low resolution broadband (200-1100 nm) fiber-optic spectrometer. This technique alleviates the need for the user to visually verify the vicinity of individual peaks during testing. While Pearson's method is generally used for this type of analysis, we show that Welch's method has the advantage of being less susceptible to problems caused by continuum background.