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The analytes, trinitrotoluene (TNT), 1,3,5\u2010trinitroperhydro\u20101,3,5\u2010triazine (RDX), 1,3,5,7\u2010tetranitroperhydro\u20101,3,5,7\u2010tetrazocine (HMX), pentaerythritol tetranitrate (PETN), nitroglycerine (NG), hexamethylene triperoxide diamine (HMTD), caffeine, cocaine and morphine, introduced through the capillary, were ionized by a low\u2010pressure air DBD. The ion source pressures were changed by using various sizes of the ion sampling orifice. The signal intensities of those analytes showed marked pressure dependence. TNT was detected with higher sensitivity at lower pressure but vice versa for other analytes. For all analytes, a marked signal enhancement was observed when a grounded cylindrical mesh electrode was installed in the DBD ion source. Among nine analytes, RDX, HMX, NG and PETN could be detected as cluster ions [analyte\u2009+\u2009NO<jats:sub>3<\/jats:sub>]<jats:sup>\u2212<\/jats:sup> even at low pressure and high temperature up to 180\u2009\u00b0C. The detection indicates that these cluster ions are stable enough to survive under present experimental conditions. The unexpectedly high stabilities of these cluster ions were verified by density functional theory calculation. 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