Ultrahigh Sensitivity PTR-MS Instrument with a Well-Defined Ion Chemistry

Abstract

Proton-transfer-reaction mass spectrometry (PTR-MS) is widely used for measuring organic trace gases in air. In traditional PTR-MS, both nonpolar and polar analytes are ionized with unit efficiency, as predicted from ion-molecule collision theories. This well-defined ion chemistry allows for direct quantification of analytes without prior calibration and therefore is an important characteristic of PTR-MS. In an effort to further increase the sensitivity, recently developed ultrahigh sensitivity chemical ionization mass spectrometry (CIMS) analyzers have, however, been reported to have sacrificed unit ionization efficiency for selected analytes or classes of analytes. We herein report on the development of a novel ultrasensitive PTR-MS instrument, the FUSION PTR-TOF 10k, which exhibits the same universal unit response as conventional PTR-MS analyzers. The core component of this analyzer is the newly designed FUSION ion-molecule reactor, which is a stack of concentric ring electrodes generating a static longitudinal electric field superimposed by a focusing transversal radiofrequency (RF) field. The FUSION PTR-TOF 10k instrument is equipped with an improved ion source, capable of switching between different reagent ions (H3O+, O2+, NO+, NH4+) in less than one second. The improved time-of-flight mass spectrometer analyzes m/z signals with a mass resolution in the 10000–15000 range. FUSION PTR-TOF 10k achieves sensitivities up to 80000 cps ppbV–1 and detection limits down to 0.5 pptV for a 1 s measurement time. We show time-series of naphthalene and 13C-napthalene as measured in ambient air in Innsbruck for demonstrating the sub-pptV detection capability of this novel FUSION PTR-TOF 10k.