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].

A tandem ion mobility spectrometer (IMS2) built from two differential mobility analyzers (DMAs) is coupled at ambient pressure with a thermal fragmenter placed in between, such that the precursor ions selected in the first DMA are thermally decomposed at ambient pressure in the fragmenter and the product ions generated are filtered in the second DMA. A thermal desorber and a multicapillary gas chromatography (GC) column are coupled to a secondary electrospray (SESI) ion source, so the adsorption sampling filters are thermally desorbed and the liberated vapors are separated in the GC column, prior to their ionization and mobility/mobility classification. The new fragmenter allows the fragmentation of the five explosives studied: RDX, PETN, NG, EGDN, and TNT. The background of the analyzer is evaluated for the five explosives using air samples of 500 L volume. An atmospheric background of only 2.5 pg (5 ppq) is found for TNT, being somewhat higher for the rest of explosives studied. The architecture GC-IMS2 is compared with GC-IMS obtaining a 100-fold increase of sensitivity in the first configuration, confirming the high selectivity provided by the fragmentation cell and the second IMS stage for the product ion mobility analysis. The analyzer is tested also with real explosives hidden in cargo pallets achieving successful detection of four (EGDN, NG, TNT, and PETN) out of five explosives.