Emissions of volatile organic compounds inferred from airborne flux measurements over a megacity

Abstract. Toluene and benzene are used for assessing the ability to measure disjunct eddy covariance (DEC) fluxes of Volatile Organic Compounds (VOC) using Proton Transfer Reaction Mass Spectrometry (PTR-MS) on aircraft. Statistically significant correlation between vertical wind speed and mixing ratios suggests that airborne VOC eddy covariance (EC) flux measurements using PTR-MS are feasible. City-average midday toluene and benzene fluxes are calculated to be on the order of 15.5±4.0 mg/m2/h and 4.7±2.3 mg/m2/h respectively. These values argue for an underestimation of toluene and benzene emissions in current inventories used for the Mexico City Metropolitan Area (MCMA). Wavelet analysis of instantaneous toluene and benzene measurements during city overpasses is tested as a tool to assess surface emission heterogeneity. High toluene to benzene flux ratios above an industrial district (e.g. 10–15) including the International airport (e.g. 3–5) and a mean flux (concentration) ratio of 3.2±0.5 (3.9±0.3) across Mexico City indicate that evaporative fuel and industrial emissions play an important role for the prevalence of aromatic compounds. Based on a tracer model, which was constrained by BTEX (Benzene/Toluene/Ethylbenzene/m,p,o-Xylenes) compound concentration ratios, the fuel marker methyl-tertiary-butyl-ether (MTBE) and the biomass burning marker acetonitrile (CH3CN), we show that a combination of industrial, evaporative fuel, and exhaust emissions account for >90% of all BTEX sources. Our observations suggest that biomass burning emissions play a minor role for the abundance of BTEX compounds (0–10%) in the MCMA.