In Situ Measurements of Atmospheric Nitrous Acid by Chemical Ionization Mass Spectrometry Using Chloride Ion Transfer Reactions

Abstract

Recently, chemical ionization mass spectrometry (CIMS) has been widely applied to the in situ measurements of atmospheric trace species. In this article, we propose a new chemical ionization scheme using a chloride ion transfer reaction from SO(2)Cl(-) as the reagent ion and discuss the applicability of this technique to the detection of nitrous acid (HONO) in the atmosphere. From laboratory investigations, the detection sensitivity was found to depend on the flow rate of SO(2) introduced into the ion source region and the pressure inside the chemical ionization region, which suggests that the chemical ionization reaction is reversible. The detection sensitivity was well described in terms of the forward and backward rates. The present limit of detection is estimated to be 60 parts per trillion by volume (pptv) for an integration time of 1 min. Improvement of the CIMS instrument would enable the measurements of the daytime level of HONO, which might be less than 50 pptv. In addition, the possibility of the interference is discussed from thermodynamic considerations based on ab initio calculations, and the effects of the sampling artifacts are experimentally quantified.