Formaldehyde total column densities over Mexico City: comparison between multi-axis differential optical absorption spectroscopy and solar-absorption Fourier transform infrared measurements

Abstract

Formaldehyde (HCHO) total column densities over the Mexico City metropolitan area (MCMA) were retrieved using two independent measurement techniques: multi-axis differential optical absorption spectroscopy (MAX-DOAS) and Fourier transform infrared (FTIR) spectroscopy. For the MAX-DOAS measurements, the software QDOAS was used to calculate differential slant column densities (dSCDs) from the measured spectra and subsequently the Mexican MAX-DOAS fit (MMF) retrieval code to convert from dSCDs to vertical column densities (VCDs). The direct solar-absorption spectra measured with FTIR were analyzed using the PROFFIT (PROFile FIT) retrieval code. Typically the MAX-DOAS instrument reports higher VCDs than those measured with FTIR, in part due to differences found in the ground-level sensitivities as revealed from the retrieval diagnostics from both instruments, as the FTIR and the MAX-DOAS information do not refer exactly to the same altitudes of the atmosphere. Three MAX-DOAS datasets using measurements conducted towards the east, west or both sides of the measurement plane were evaluated with respect to the FTIR results. The retrieved MAX-DOAS HCHO VCDs where 6 %, 8 % and 28 % larger than the FTIR measurements which, supported with satellite data, indicates a large horizontal inhomogeneity in the HCHO abundances. The temporal change in the vertical distribution of this pollutant, guided by the evolution of the mixing-layer height, affects the comparison of the two retrievals with different sensitivities (total column averaging kernels). In addition to the reported seasonal and diurnal variability of HCHO columns within the urban site, background data from measurements at a high-altitude station, located only 60 km away, are presented.