Fast-response airborne in situ measurements of HNO3 during the Texas 2000 Air Quality Study

Nitric acid (HNO3) was measured from an aircraft in the planetary boundary layer and free troposphere up to 7 km on 14 flights during the Texas Air Quality Study in August and September 2000. HNO3 mixing ratios were measured at 1 Hz using a fast‐response chemical ionization mass spectrometer with SiF5− reagent ions. HNO3 measurement using this highly selective ion chemistry is insensitive to water vapor and is not degraded by interferences from other species. Rapid time response (1 s) was achieved using a heated Teflon inlet. In‐flight standard addition calibrations from a HNO3 permeation source were used to determine the instrument sensitivity of 1.1 ± 0.1 ion counts pptv−1 s−1 over the duration of the study. Contributions to the HNO3 signal from instrument artifacts were accounted for by regularly performing in‐flight instrument background checks, where HNO3 was removed from the ambient air sample by diverting the sampled air though a nylon wool scrubber. Measurement inaccuracy, which is determined from uncertainties in the standard addition calibrations, was ±10%. Measurement precision at low HNO3 levels was ±25 pptv (1σ) for the 1 Hz data and ±9 pptv for 10 s averages of the 1 s measurements. Coincident in situ measurements of other reactive nitrogen species are used to examine NOy partitioning and HNO3 formation during this month long measurement campaign. The sum of the individually measured reactive nitrogen species is shown to be in agreement with the measured NOy. HNO3 formation in plumes from electric utility power plants, urban areas, and petrochemical facilities was studied. The observed differences in the fractional contribution of HNO3 to NOy in plumes from different anthropogenic source types are discussed.