Laboratory and field characterization of an atmospheric pressure transverse chemical ionization ion-molecule reaction region

Abstract. We introduce a custom-built, field-deployable, atmospheric pressure Ion-Molecule reaction Region (IMR) for use with Chemical Ionization Mass Spectrometry (CIMS), the so-called “t-IMR”. The design is described in quantitative detail and shows significant mitigation in potential measurement interference compared to other IMR configurations, particularly those operating at low pressure. The relatively large laminar flow and inner chamber diameter reduce the probability of sampled air and ion clusters interacting with the Teflon surfaces of the IMR before being detected by Time-of-Flight (ToF) mass spectrometry. This also leads to a substantial reduction in wall effects and artificial background signals for even low volatility organic products, as demonstrated in alpha-pinene ozonolysis experiments. An electric field is induced perpendicular to flow in the t-IMR to accelerate ions and consequent charged sample clusters to the MS interface. The strength of this field is modulated and optimized to simultaneously maximize total ion flux and instrument sensitivity. A sheath flow apparatus is introduced to provide small N2 flows counter to ion and sample cluster flow into the MS to reduce the likelihood of particulate buildup and clogs to the pinhole separating the IMR from the MS, ensuring uninterrupted sampling for extended periods of time. Finally, we demonstrate the capability of the t-IMR to be deployed to the field to measure down to sub-ppt level ambient concentrations of important trace gases including reactive bromine at a ground-based site in the marine boundary layer. We find that the t-IMR design considerably reduces artificial signals from surface contact and wall effects, and improves detection of very low concentration species in the ambient atmosphere, with respective limits of detection of 0.06, 0.05, and 2 ppt for Br2, HOBr, and HNO3. The relationship between instrument sensitivity and IMR water vapor concentrations is also explored and applied to in-field measurements.