A Chemical Ionization Mass Spectrometer for Ambient Measurements of Ammonia

This study presents a chemical ionization mass spectrometer (CIMS) for fast response, in-situ measurements of gas phase ammonia (NH3). The NH3 background level detected with the CIMS ranged between 0.3–1 ppbv, with an uncertainty of 30 pptv under optimized conditions. The instrument sensitivity varied from 4–25 Hz/pptv for >1 MHz of reagent ion signals (protonated ethanol ions), with a 30% uncertainty estimated based on variability in calibration signals. The CIMS detection limit for NH3 was ∼60 pptv at a 1 min integration time (3 sigma). The CIMS time response was <30 s. This new NH3-CIMS has been used for ambient measurements in Kent, Ohio, for several weeks throughout three seasons. The measured NH3 mixing ratios were usually at the sub-ppbv level and higher in spring (200±120 pptv) than in winter (60±75 pptv) and fall (150±80 pptv). High emissions of SO2 from power plants in this region, and thus possible high acidity of aerosol particles, may explain these low NH3 mixing ratios in general.