RESUMO
Nitrous acid (HONO) is a major precursor of tropospheric hydroxyl radical (OH) that accelerates the formation of secondary pollutants. The HONO sources, however, are not well understood, especially in polluted areas. Based on a comprehensive winter field campaign conducted at a rural site of the North China Plain, a box model (MCM v3.3.1) was used to simulate the daytime HONO budget and nitrate formation. We found that HONO photolysis acted as the dominant source for primary OH with a contribution of more than 92%. The observed daytime HONO could be well explained by the known sources in the model. The heterogeneous conversion of NO2 on ground surfaces and the homogeneous reaction of NO with OH were the dominant HONO sources with contributions of more than 36 and 34% to daytime HONO, respectively. The contribution from the photolysis of particle nitrate and the reactions of NO2 on aerosol surfaces was found to be negligible in clean periods (2%) and slightly higher during polluted periods (8%). The relatively high OH levels due to fast HONO photolysis at the rural site remarkably accelerated gas-phase reactions, resulting in the fast formation of nitrate as well as other secondary pollutants in the daytime.
Assuntos
Nitratos , Ácido Nitroso , Aerossóis , China , Radical Hidroxila , Ácido Nitroso/análiseRESUMO
The Weather Research and Forecasting/Chemistry (WRF-Chem) model updated with six potential HONO sources (i.e., traffic, soil, biomass burning and indoor emissions, and heterogeneous reactions on aerosol and ground surfaces) was used to quantify the impact of the six potential HONO sources on the production and loss rates of OH and HO2 radicals and the concentrations of secondary organic aerosol (SOA) in the Beijing-Tianjin-Heibei (BTH) region of China during a winter heavy haze period of Nov. 29-Dec. 3, 2017. The updated WRF-Chem model well simulated the observed HONO concentrations at the Wangdu site, especially in the daytime, and well reproduced the observed diurnal variations of regional-mean O3 in the BTH region. The traffic emission source was an important HONO source during nighttime but not significant during daytime, heterogeneous reactions on ground/aerosol surfaces were important during nighttime and daytime. We found that the six potential HONO sources led to a significant enhancement in the dominant production and loss rates of HOx on the wintertime heavy haze and nonhaze days (particularly on the heavy haze day), an enhancement of 5-25⯵gâ¯m-3 (75-200%) in the ground SOA in the studied heavy haze event, and an enhancement of 2-15⯵gâ¯m-3 in the meridional-mean SOA on the heavy haze day, demonstrating that the six potential HONO sources accelerate the HOx cycles and aggravate haze events. HONO was the key precursor of primary OH in the BTH region in the studied wintertime period, and the photolysis of HONO produced a daytime mean OH production rate of 2.59â¯ppbâ¯h-1 on the heavy haze day, much higher than that of 0.58â¯ppbâ¯h-1 on the nonhaze day. Anthropogenic SOA dominated in the BTH region in the studied wintertime period, and its main precursors were xylenes (42%), BIGENE (31%) and toluene (21%).