Miniature mass spectrometers are powerful tools for on-site chemical analysis in the fields of homeland security, personal healthcare, and environmental monitoring. This study presents a novel hexapole-assisted continuous atmospheric pressure interface for a high-pressure photoionization miniature ion trap mass spectrometer (HA-HPPI-IT). Efficient ion transmission was achieved by combining radial focusing by an RF electric field and axial driving by gas flow, which was demonstrated by SIMION simulation and experimental verification. The pressure in the ionization-transmission chamber and the inner diameter of the skimmer were optimized, which helped in determining the number density of product ions and affected the ion transmission in the hexapole, respectively. After systematic optimizations, about 16-fold increase in signal intensity was achieved as the RF amplitude was varied from 140 to 400 Vpp, and a limit of detection of 1 ppbv was obtained. In addition, the HA-HPPI-IT exhibited high stability and the relative standard deviation was as low as 5.47%. Finally, the apparatus was applied for discovering the simulated spot for illicit drug synthesis by detecting toluene and propiophenone released to air and monitoring the evolutions of perchloroethylene residues from dry-cleaned clothes.

Discontinuous atmospheric pressure interface (DAPI) consisting of a pinch valve, a silicone tube, and two metal capillaries has been widely used in miniature mass spectrometry. It is interesting that clear ion signals could be observed even when the extra ionization source was turned off. In-depth analysis suggested that this new ionization phenomenon known as triboionization is based on the surface friction on the inner surface of the silicone tube during the on/off of the pinch valve. In this study, triboionization in the DAPI of a miniature ion trap mass spectrometer was investigated. It was discovered that the signal intensity depended greatly on the material and the roughness of the silicone tube used in the DAPI. By rubbing the inner surface of the silicone tube, for example, the signal intensity can increase by nearly 20 times. Two connected pinch valves were developed to study the effects of the discharge pressure, the number, and the frequency of on/off of the pinch valve on triboionization, which were verified to have a large impact on the product ions. In addition, the humidity of the inner surface of the silicone tube impacted the signal intensity of product ions and the mass spectrum patterns, where the product ions were typically protonated ions. As the humidity increases, the signal intensity of analytes with high proton affinity increases accordingly. This triboionization source, which does not require heat, light, radiation, auxiliary gas, or solution, has been preliminarily proved to have potential for surface detection after continuous enrichment.