Heterogeneous photochemical uptake of NO₂ on the soil surface as an important ground-level HONO source

Nitrous acid (HONO) production from the heterogeneous photochemical reaction of NO₂ on several Chinese soils was performed in a cylindrical reactor at atmospheric pressure. The NO₂ uptake coefficient (γ) and HONO yield (Y_HONO) on different soils were (0.42-5.16) × 10^-5 and 6.3%-69.6%, respectively. Although the photo-enhanced uptake of NO₂ on different soils was observed, light could either enhance or inhibit the conversion efficiency of NO₂ to HONO, depending on the properties of the soils. Soils with lower pH generally had larger γ and Y_HONO. Soil organics played a key role in HONO formation through the photochemical uptake of NO₂ on soil surfaces. The γ showed a positive correlation with irradiation and temperature, while it exhibited a negative relationship with relative humidity (RH). Y_HONO inversely depended on the soil mass (0.32-3.25 mg cm^-2), and it positively relied on the irradiance and RH (7%-22%). There was a maximum value for Y_HONO at 298 K. Based on the experimental results, HONO source strengths from heterogeneous photochemical reaction of NO₂ on the soil surfaces were estimated to be 0.2-2.7 ppb h^-1 for a mixing layer height of 100 m, which could account for the missing daytime HONO sources in most areas.