Emission Ratios and Source Identification of VOCs in Moscow in 2019–2020

Abstract

Measurements of CO and 15 volatile organic compounds (VOCs) at the IAP-RAS (A.M. Obukhov Institute of Atmospheric Physics) site located in the center of Moscow were analyzed. Acetaldehyde, ethanol, 1.3-butadiene, isoprene, toluene and C-8 aromatics were established to be the main ozone precursors in the observed area, providing up to 82% of the total ozone formation potential of the VOCs measured. Diurnal and seasonal variations of the compounds are discussed. The concentrations of anthropogenic VOCs (acetaldehyde, benzene, 1.3-butadiene, toluene, and C-8 aromatics) did not exceed their maximum permissible levels, reaching their maxima in summer and autumn in the morning and evening hours. Biogenic ethanol and isoprene were the highest in summer midday but their concentrations were low enough (up to 4 and 0.4 ppbv, respectively) due to small vegetation area around the site. Emission ratios (ERs) for the main ozone precursors— acetaldehyde, ethanol, 1.3-butadiene, isoprene, toluene, and C-8 aromatics—were estimated from two-sided linear regression fits using benzene and CO as tracers for anthropogenic emissions, with spatial and temporal filters being applied to account for the influence of chemistry and local emission sources. The best estimates of ERs were obtained using benzene as a reference species. Anthropogenic fractions of VOCs (AFs) were then estimated. As expected, acetaldehyde, toluene, 1.3-butadiene, and C8aromatics were entirely anthropogenic and emitted mainly from urban vehicle exhausts throughout the day, both in summer and in winter. AFs of isoprene and ethanol did not exceed 30% and 50% in summer, respectively, during both daytime and nighttime hours. In winter, the anthropogenic fractions of isoprene and ethanol were slightly higher (up to 35% and 60%, respectively).