Airborne formaldehyde measurements using PTR-MS: calibration, humidity dependence, inter-comparison and initial results

Abstract

Abstract. We present quantitative, fast time response measurements of formaldehyde (HCHO) onboard an aircraft using a Proton-Transfer-Reaction Mass-Spectrometry (PTR-MS) instrument. The HCHO measurement by PTR-MS is strongly humidity dependent and therefore airborne measurements are difficult and have not been reported. The PTR-MS instrument was run in the standard PTR-MS operating mode (de Gouw and Warneke, 2007), where about 15 volatile organic compounds (VOCs) are measured together with HCHO onboard the NOAA WP-3 aircraft during the CalNex 2010 campaign in California. We compare the humidity dependence determined in the laboratory with in-flight calibrations of HCHO and calculate the HCHO mixing ratio during all flights using the results from both. The detection limit (S/N = 1) for HCHO was between 100 pptv in the dry free troposphere and 300 pptv in the humid marine boundary layer for a one second acquisition time every 17 s. The PTR-MS measurements are compared with HCHO measurements using a DOAS instrument and a Hantzsch monitor at a ground site in Pasadena. The PTR-MS agreed with the DOAS within the stated uncertainties and was just outside the uncertainties with the Hantzsch. We also compare HCHO enhancement ratios in the Los Angeles basin and in the free troposphere with literature values and find good agreement. The usefulness of the PTR-MS HCHO measurements in atmospheric observations is demonstrated by following an isolated anthropogenic plume. The photochemical production of HCHO can be observed simultaneously with production of acetaldehyde and the photochemical degradation of aromatic compounds using the PTR-MS. The results show that PTR-MS seems a useful instrument to measure HCHO, but more inter-comparisons are needed.