Primary sources of HONO vary during the daytime: Insights based on a field campaign

Nitrous acid (HONO) is an established precursor of hydroxyl (OH) radical and has significant impacts on the formation of PM_2.5 and O₃. Despite extensive research on HONO observation in recent years, knowledge regarding its sources and sinks in urban areas remains inadequate. In this study, we monitored the atmospheric concentrations of HONO and related pollutants, including gaseous nitric acid and particulate nitrate, simultaneously at a supersite in downtown Chengdu, a megacity in southwestern China during spring, when was chosen due to its tolerance for both PM_2.5 and O₃ pollution. Furthermore, we employed the random forest model to fill the missing data of HONO, which exhibited good predictive performance (R² = 0.96, RMSE = 0.36 ppbv). During this campaign, the average mixing ratio of HONO was measured to be 1.0 ± 0.7 ppbv. Notably, during periods of high O₃ and PM_2.5 concentrations, the mixing ratio of HONO was >50 % higher compared to the clean period. We developed a comprehensive parameterization scheme for the HONO budget, and it performed well in simulating diurnal variations of HONO. Based on the HONO budget analysis, we identified different mechanisms that dominate HONO formation at different times of the day. Vehicle emissions and NO₂ heterogeneous conversions were found to be the primary sources of HONO during nighttime (21.0 %, 30.2 %, respectively, from 18:00 to 7:00 the next day). In the morning (7:00-12:00), NO₂ heterogeneous conversions and the reaction of NO with OH became the main sources (35.0 %, 32.2 %, respectively). However, in the afternoon (12:00-18:00), the heterogeneous photolysis of HNO₃ on PM_2.5 was identified as the most substantial source of HONO (contributing 52.5 %). This study highlights the significant variations in primary HONO sources throughout the day.