Abstract: Apparatus and methods for selectively separating a volatile constituent of a particle from a gas stream for analysis. Particles are separated from bulk flow by inertia and impacted in a cavity containing a small but stable vortex or eddy. Heat is applied to volatilize constituents of the particles. The gas entrained within the vortex, which exchanges only slowly with the bulk flow, is withdrawn for analysis. In this way, a high volume flow containing particles of interest is reduced to a low volume flow containing a vapor concentrate. Advantageously, the apparatus may be operated at very low pressure drops in fully continuous, semi-continuous or batch mode according to the requirements of the downstream analytical unit. The apparatus finds use in active surveillance, such as in use of aerosols to detect explosives or chemical residues on persons, vehicles or luggage in real time.