Comparison of negative-ion proton-transfer with iodide ion chemical ionization mass spectrometry for quantification of isocyanic acid in ambient air

Abstract Isocyanic acid (HNCO) is a trace gas pollutant of potential importance to human health whose measurement has recently become possible through the development of negative-ion proton-transfer chemical ionization mass spectrometry (NI-PT-CIMS) with acetate reagent ion. In this manuscript, an alternative ionization and detection scheme, in which HNCO is quantified by iodide CIMS (iCIMS) as a cluster ion at m / z 170, is described. The sensitivity was inversely proportional to water vapor concentration but could be made independent of humidity changes in the sampled air by humidifying the ion–molecule reaction (IMR) region of the CIMS. The performance of the two ionization schemes was compared and contrasted using ambient air measurements of HNCO mixing ratios in Calgary, AB, Canada, by NI-PT-CIMS with acetate reagent ion from Dec 16 to 20, 2013, and by the same CIMS operated in iCIMS mode from Feb 3 to 7, 2014. The iCIMS exhibited a greater signal-to-noise ratio than the NI-PT-CIMS, not because of its sensitivity, which was lower (∼0.083 normalized counts per second (NCPS) per parts-per-trillion by volume (ppt v ) compared to ∼9.7 NCPS ppt v −1 ), but because of a much lower and more stable background (3 ± 4 compared to a range of ∼2 × 10 3 to ∼6 × 10 3  NCPS). For the Feb 2014 data set, the HNCO mixing ratios in Calgary air ranged from v (median 34 ppt v ), were marginally higher at night than during day, and correlated with nitrogen oxide (NO x  = NO + NO 2 ) mixing ratios and submicron particle volume. The ratios of HNCO to NO x observed are within the range of emission ratios reported for gasoline-powered motor vehicles.