The feasibility of detecting explosives in the atmosphere at concentrations as low as 0.01 ppq hinges on the poorly known question of what interfering species exist at these or higher concentrations. To clarify the issue, hundreds of samples of ambient air, either clean or loaded with explosives (from lightly contaminated environments) have been collected in fiberglass/stainless steel filters coated with Tenax-GR, thermally desorbed at variable temperature, and ionized with Cl via secondary electrospray (SESI). They are analyzed with a narrow-band mobility filter (SEADM's P5 DMA) and a triple quadrupole mass spectrometer (Sciex's 5500), configured in series to transmit precursor and fragment ions of the explosives Nitroglycerin, PETN, RDX, and TNT. Blanks were sampled outdoors at a rural site (Boecillo, Valladolid, Spain), and loads were sampled at diverse locations. For RDX and TNT, atmospheric background inhibits detection below 1 part/trillion (ppt) without mobility filtering. This interference was drastically reduced by the DMA, allowing detection up to 1 part/quadrillion (ppq). Further sensitivity increase was achieved by scanning over a mobility region several percent around that of the target explosive, to separate various isobaric compounds by Gaussian deconvolution. (i) All four MS/MS channels analyzed exhibit several background peaks within the narrow mobility intervals investigated. At least one of these interferents is much stronger than the instrument background at the explosive's mobility, making DMA separation most helpful. (ii) For Nitroglycerin and PETN the combined filtering techniques have not lowered ambient chemical noise down to 0.01 ppq. (iii) Interferents are greatly reduced for TNT and RDX, resulting in minimal chemical noise: 322 blank tests for RDX yielded mean signal of 0.0012 ppq and standard deviation σ = 0.0035 ppq (mean + 3σ detection limit of 0.01 ppq).
Planar differential mobility analyzers (DMAs) have previously achieved resolving powers of 60-80 in air or N at the mobility of the tetraheptylammonium ion (THA, ∼0.97 cm/V/s). For unclear reasons, this performance is considerably below the theoretical limit. In this work, a performance close to this ideal limit is attained in SEADM's P5 DMA via improved flow laminarization, under otherwise the same flow conditions as in prior work. The new laminarizer remains effective at unusually large gas velocities (reached with two blowers in series), yielding a resolving power of 110. The selectivity of the improved DMA combined with a mass spectrometer was assessed by the analysis of a real sample of extra virgin olive oil.
The differential mobility analyzer (DMA) is a narrow-band linear ion mobility filter operating at atmospheric pressure. It combines in series with a quadrupole mass spectrometer (Q-MS) for mobility/mass analysis, greatly reducing chemical noise in selected ion monitoring. However, the large flow rate of drift gas (~1000 L/min) required by DMAs complicates the achievement of high gas purity. Additionally, the symmetry of the drying counterflow gas at the interface of many commercial MS instruments, is degraded by the lateral motion of the drift gas at the DMA entrance slit. As a result, DMA mobility peaks often exhibit tails due to the attachment of impurity vapors, either (1) to the reagent ion within the separation cell, or (2) to the analyte of interest in the ionization region. In order to greatly increase the noise-suppression capacity of the DMA, we describe various vapor-removal schemes and measure the resulting increase in the tailing ratio, (TR = signal at the peak maximum over signal two half-widths away from this maximum). Here we develop a low-outgassing DMA circuit connected to a mass spectrometer, and test it with three ionization sources (APCI, Desolvating-nano ESI, and Desolvating low flow SESI). While prior TR values were in the range 100-1000, the three new sources achieve TR ~ 10. The SESI source has been optimized for maximum sensitivity, delivering an unprecedented gain for TNT of 190 counts/fg, equivalent to an ionization efficiency of one out of 140 neutral molecules. Graphical Abstract ᅟ.
Two differential mobility analyzers (DMAs) acting as narrow band mobility filters are coupled in series, with a thermal fragmentation cell placed in between, such that parent ions selected in DMA are fragmented in the cell at atmospheric pressure, and their product ions are analyzed on DMA. Additional mass spectrometer analysis is performed for ion identification purposes. A key feature of the tandem DMA is the short residence time (∼0.2 ms) of ions in the analyzer, compared to tens of milliseconds in drift tube ion mobility spectrometers (IMS). Ion fragmentation within the analyzer and associated mobility tails are therefore negligible for a DMA but not necessarily so in conventional IMS. This advantage of the DMA is demonstrated here by sharply defined product ion mobility peaks. Ambient pressure ion fragmentation has been previously demonstrated by both purely thermal means as well as rapidly oscillating intense electric fields. Our purely thermal fragmentation cell here achieves temperatures up to 700 °C measured inside the heating coil of a cylindrical ceramic heater, through whose somewhat colder axis we direct a beam of mobility-selected ions. We investigate tandem separation of chloride adducts from the explosives EGDN, nitroglycerine (NG), PETN, and RDX and from deprotonated TNT. Atmospheric pressure fragmentation of the first three ions yields one or several previously reported fragments, providing highly distinctive tandem DMA channels for explosive identification at 1 atm. RDX ions had not been previously fragmented at ambient pressure, yet [RDX + Cl] converts up to 7% (at 300 °C) into a 166 m/ z product. The known high thermal resilience of TNT is confirmed here by its rather modest conversion, even when the ceramic is heated to 700 °C. At this temperature some previously reported fragments are found, but their mobilities are fairly close to each other and to the one of the far more abundant parent ion, making their identification by mobility alone problematic. We anticipate that moderately higher fragmenter temperatures will produce smaller fragments with mobilities readily separated from that of [TNT - H].
Two fast electrometer circuits (10 11 and 10 12 V/A) are installed in a Faraday cage having a relatively small residence time. Removing readily distinguishable occasional spikes, the root mean square (r. m.s.) noise level at 10 12 V/A is 0.11 fA when acquiring data at 1 Hz. This value is close to the expected thermal resistor noise at room temperature (0.09 mV). Both electrometers exhibit a 20 ms flow-related delay, followed by respective half-height rise-times of »4 and 25 ms. Fast highresolution mobility spectra in the 1-2 nm size range are acquired with electrosprayed tetraheptylammonium ions by combining these electrometers with a high-speed DMA. At 10 12 V/A, there is no ion mobility peak distortion when acquiring data with discrete voltage steps and dwelling 100 ms at each voltage. With the 10 11 V/A electrometer, the DMA voltage V DMA is continuously swept up and down over 600 V in a triangular wave, at up to 1200 V/s. A shift DV DMA in the peak center is apparent, with little peak shape distortion. DV DMA is symmetric with respect to up or down sweep, and linear with sweep frequency, corresponding approximately to a pure delay Dt D 25 ms. This peak displacement may be offset by adding the correction DV DMA D Dt (dV DMA /dt) to the measured peak voltage. Extrapolating the measurements made here over a mobility range Z max /Z min of 4 to a much wider mobility range of 300 typical of aerosol studies, we conclude that almost undistorted high-resolution mobility spectra may be acquired in 1.3 s.
scite is a Brooklyn-based organization that helps researchers better discover and understand research articles through Smart Citations–citations that display the context of the citation and describe whether the article provides supporting or contrasting evidence. scite is used by students and researchers from around the world and is funded in part by the National Science Foundation and the National Institute on Drug Abuse of the National Institutes of Health.
hi@scite.ai
10624 S. Eastern Ave., Ste. A-614
Henderson, NV 89052, USA
Copyright © 2024 scite LLC. All rights reserved.
Made with 💙 for researchers
Part of the Research Solutions Family.