MAX-DOAS measurements and vertical profiles of glyoxal and formaldehyde in Madrid, Spain

Glyoxal (CHOCHO) and formaldehyde (HCHO) are organic trace gases that play an important role in tropospheric chemistry as oxidation products of a number of volatile organic compounds (VOCs). In this study, we report year-round daytime measurements of glyoxal and formaldehyde in the urban atmosphere of Madrid, Spain. Their vertical concentration profiles were retrieved using the Multi AXis Differential Optical Absorption Spectroscopy (MAX-DOAS) technique and a Radiative Transfer Model (RTM) that simulates solar photon paths through the atmosphere. The diurnal variations of HCHO show two distinct peaks during the day, in the early morning and late afternoon in spring and summer, while the second peak is shifted towards noon in autumn and winter, due to lower photolysis rates and more effective boundary layer accumulation of HCHO in those seasons. The HCHO surface mixing ratios range from 6 ppbv to 27 ppbv in spring-summer and from 10 ppbv to 30 ppbv in autumn-winter. Monthly hourly-averaged glyoxal surface mixing ratios in the early morning show higher values during winter, 2 ppbv, than in summer, 0.7 ppbv. We also evaluated the ratio between glyoxal and formaldehyde (R-GF) surface mixing ratios, as an indicator of the nature of VOCs precursors. The R-GF was also correlated with the measured NO2, which represents a direct signal of anthropogenic emissions, along with the VOCs emission inventories in Madrid. The Et u results yielded higher ratios in spring, 0.1-0.13, than in winter and autumn (in the range of 0.02-0.07) when NO2 levels were higher.