Airborne observations of formic acid using a chemical ionization mass spectrometer

Abstract

The first airborne measurements of formic acid mixing ratios over the United Kingdom were measured on the FAAM BAe-146 research aircraft on 16 March 2010 with a chemical ionization mass spectrometer using I^&minus; reagent ions. The I^&minus; ionization scheme was able to measure formic acid mixing ratios at 1 Hz in the boundary layer. <br><br> In-flight standard addition calibrations from a formic acid source were used to determine the instrument sensitivity of 35 &plusmn; 6 ion counts pptv⁻¹ s⁻¹ and a limit of detection of 25 pptv. Routine measurements were made through a scrubbed inlet to determine the instrumental background. Three plumes of formic acid were observed over the UK, originating from London, Humberside and Tyneside. The London plume had the highest formic acid mixing ratio throughout the flight, peaking at 358 pptv. No significant correlations of formic acid with NO_x and ozone were found, but a positive correlation was observed between CO and HCOOH within the two plumes where coincident data were recorded. <br><br> A trajectory model was employed to determine the sources of the plumes and compare modelled mixing ratios with measured values. The model underestimated formic acid concentrations by up to a factor of 2. This is explained by missing sources in the model, which were considered to be both primary emissions of formic acid of mainly anthropogenic origin and a lack of precursor emissions, such as isoprene, from biogenic sources, whose oxidation in situ would lead to formic acid formation.