Contribution of Vehicle Emission and NO₂ Surface Conversion to Nitrous Acid (HONO) in Urban Environments: Implications from Tests in a Tunnel

Nitrous acid (HONO) is an important photochemical precursor to hydroxyl radicals particularly in an urban atmosphere, yet its primary emission and secondary production are often poorly constrained. Here, we measured HONO and nitrogen oxides (NOx) at both the inlet and the outlet in a busy urban tunnel (>30 000 vehicles per day) in south China. Multiple linear regression revealed that 73.9% of the inlet-outlet incremental HONO concentration was explained by NO2 surface conversion, while the rest was directly emitted from vehicles with an average HONO/NOx ratio of 1.31 ± 0.87%, which was higher than that from previous tunnel studies. The uptake coefficient of NO2, γ(NO2), on the tunnel surfaces was calculated to be (7.01 ± 0.02) × 10-5, much higher than that widely used in models. As tunnel surfaces are typical of urban surfaces in the wall and road materials, the dominance of HONO from surface reactions in the poorly lit urban tunnel demonstrated the importance of NO2 conversion on urban surfaces, instead of NO2 conversion on the aerosol surface, for both daytime and night-time HONO even in polluted ambient air. The higher γ(NO2) on urban surfaces and the elevated HONO/NOx ratio from this study can help explain the missing HONO sources in urban areas.