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Nitrous acid (HONO) can be photolyzed to produce hydroxyl radicals (OH) in the atmosphere. OH plays a critical role in the formation of secondary pollutants like ozone (O 3 ) and secondary organic aerosols (SOA) via various oxidation reactions. Despite the abundance of recent HONO studies, research on national HONO emissions in China remains relatively limited. Therefore, this study employed a "wetting-drying" model and bottom-up approach to develop a high-resolution gridded inventory of HONO emissions for mainland China using multiple data. We used the Monte Carlo method to estimate the uncertainty in HONO emissions. In addition, the primary sources of HONO emissions were identified and their spatiotemporal distribution and main influencing factors were studied. The results indicated that the total HONO emissions in mainland China in 2016 were 0.77 Tg N (R 50 : 0.28-1.42 Tg N), with soil (0.42 Tg N) and fertilization (0.26 Tg N) as the primary sources, jointly contributing to over 87% of the total. Notably, the North China Plain (NCP) had the highest HONO emission density (3.51 kg N/ha/yr). Seasonal HONO emissions followed the order: summer (0.38 kg N/ha) > spring (0.19 kg N/ha) > autumn (0.17 kg N/ha) > winter (0.06 kg N/ha). Moreover, HONO emissions were strongly correlated with fertilization, cropland, temperature, and precipitation. This study provides vital scientific groundwork for the atmospheric nitrogen cycle and the formation of secondary pollutants., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2023 Elsevier Ltd. All rights reserved.)

Despite implementation of strict emission mitigation measures since 2013, heavy haze with high levels of secondary aerosols still frequently engulfs the Guanzhong Basin (GZB), China, during wintertime, remarkably impairing visibility and potentially causing severe health issues. Although the observed low ozone (O 3 ) concentrations do not facilitate the photochemical formation of secondary aerosols, the measured high nitrous acid (HONO) level provides an alternate pathway in the GZB. The impact of heterogeneous HONO sources on the wintertime particulate pollution and atmospheric oxidizing capability (AOC) is evaluated in the GZB. Simulations by the Weather Research and Forecast model coupled with Chemistry (WRF-Chem) reveal that the observed high levels of nitrate and secondary organic aerosols (SOA) are reproduced when both homogeneous and heterogeneous HONO sources are considered. The heterogeneous sources (HET-sources) contribute about 98% of the near-surface HONO concentration in the GZB, increasing the hydroxyl radical (OH) and O 3 concentration by 39.4% and 22.0%, respectively. The average contribution of the HET-sources to SOA, nitrate, ammonium, and sulfate in the GZB is 35.6%, 20.6%, 12.1%, and 6.0% during the particulate pollution episode, respectively, enhancing the mass concentration of fine particulate matters (PM 2.5 ) by around 12.2%. Our results suggest that decreasing HONO level or the AOC becomes an effective pathway to alleviate the wintertime particulate pollution in the GZB., (Copyright © 2022 Elsevier Ltd. All rights reserved.)

HONO is an important component of reactive nitrogen (N r ) and precursors of OH radical. However, the source and removal of HONO are not clear. Here, measurements of HONO (May 18-31, 2018) were conducted in Xi'an and Xianyang simultaneously for the first time. The relationship between HONO and other N r (such as NO and NO 2 ) in two cities was analyzed. The mixing ratio of HONO in Xi'an was 1.2 ± 0.8 ppbv, and that in Xianyang was 1.2 ± 1.1 ppbv. The nighttime HONO mixing ratio was higher in Xianyang, while the daytime HONO was higher in Xi'an. Compared with the contribution from heterogeneous process of NO 2 , direct emissions and homogeneous processes (NO + OH) were less important for nocturnal HONO formation in these two cities. The relative contribution of heterogeneous process in Xianyang was more important than that in Xi'an. The reaction of NO 2 upon aerosols surface was identified as an important source of HONO for two sites. The conversion of NO 2 on the other surfaces might attend the heterogeneous formation of HONO in Xianyang site. Daytime HONO budget analysis indicated that there was an additional unknown formation process of HONO at two sites. The net OH production rate from HONO (from 08:00 to 17:00) was 1.6 × 10 7 and 1.3 × 10 7 molecule/(cm 3 s) for Xian and Xianyang, 5.2 and 3.5 times higher than from O 3 photolysis. Besides, a dust storm appeared during this observation period, and the impact of local emission and transport processes was separately analyzed. The sources, characteristics, and effects of HONO identified in this study laid a foundation for further research on HONO and air pollution in the Guanzhong area., (Copyright © 2021 Elsevier Ltd. All rights reserved.)

Atmospheric ammonia (NH 3 ) as the most important alkaline gas in the atmosphere has attracted much attention in recent years due to its critical role in haze formation, especially on the North China Plain (NCP). Comprehensive studies are needed for investigating diurnal variations of NH 3 and underlying mechanisms in different seasons and their potential impacts on atmospheric chemistry. In this study, continuous long-term observation (Mar. 2016 to May 2017) of NH 3 at a rural site in the NCP was used to characterize the diurnal variation of NH 3 in different seasons and to unveil its causes and potential impacts on atmospheric chemistry. NH 3 concentrations displayed rapid increases during the morning, reaching very prominent peaks mostly between 8:00 to 11:00 LT. Such frequent (55%) morning peaks were mainly caused by the evaporation of dew and guttation water droplets. Average dew and guttation water volume concentrations of 750 mL m -2 was estimated for spring, which resulted in approximate NH 3 emissions of 800 ng m -2 s - 1 . Such high emission fluxes from dew and guttation water evaporation have never been reported before, suggesting dew and guttation droplets to be significant night-time reservoirs and strong morning sources for NH 3 . In light of recent studies putting forward that NH 3 can promote the heterogeneous formation of HONO and nitrate under high humidity conditions, we investigated the differences in HONO and aerosol chemical composition diurnal variations between days with and without NH 3 morning spikes during November. HONO, nitrate and sulfate concentrations were significantly higher for days with NH 3 morning spikes, with HONO displaying a morning peak near that of NH 3 . These results demonstrate that the prevailing NH 3 morning spikes on the NCP have significant influences on aerosol formation and atmospheric chemistry. NH 3 emission mitigation strategies and regulations are urgently needed., (Copyright © 2019 Elsevier Ltd. All rights reserved.)

The generation of HONO and NO 2 by the photolysis of nitrates in the presence of humic acids (HA) was measured under various conditions. The photolysis experiments of HA, KNO 3 and KNO 3 /HA under simulated sunlight was carried out by a flow tube reactor at ambient temperature and pressure. HONO and NO 2 were major products by the photolysis of KNO 3 . By contrast, the photolysis of HA and KNO 3 /HA mainly generated HONO. HA significantly enhanced the formation of HONO during the photolysis process of KNO 3 . With increasing the KNO 3 mass, the HONO formation rate (R HONO ) on KNO 3 /HA increased while the photolysis rate normalized by the KNO 3 mass exhibited an opposite trend. R HONO on KNO 3 /HA linearly increased with irradiation intensity (88-262 W/m 2 ) and relative humidity (7-70%), whereas it linearly decreased with the pH (pH = 2-12). In addition, the reaction paths of the HONO formation by the photolysis of nitrates in the presence of HA were proposed according to experimental results. Finally, atmospheric implications of the enhanced HONO formation by the photolysis of nitrates in the presence of HA were discussed., (Copyright © 2018 Elsevier Ltd. All rights reserved.)

In this study, the formation of nitrate aerosol from 16 to 24 December 2015 in the Guanzhong basin, China is simulated using the WRF-Chem model. The predicted near-surface O 3 , NO 2 , and fine particulate matters (PM 2.5 ) in the basin and inorganic aerosols and nitrous acid (HONO) in Xi'an are generally in good agreement with the observations. Sensitivity studies show that the heterogeneous HONO sources play an appreciable role in the nitrate formation in the basin, contributing 9.2% of nitrate mass concentrations during heavy haze days. Nitrate formation is also affected by sulfate due to their competition for ammonia, particularly in urban areas. A 50% decrease in SO 2 emissions enhances the nitrate concentration by 6.2% during heavy haze days on average in the basin, and a 50% increase in SO 2 emission reduces the nitrate concentration by 9.7%. The roles of HONO and sulfate competition in nitrate formation are strongly modulated by ammonia. Agricultural emissions predominate the nitrate level in the basin (93.5%), but the non-agricultural sources cannot substantially influence nitrate formation (3.7%-14.6%). Reducing agricultural emission is an effective control strategy to mitigate nitrate pollution in the basin., (Copyright © 2018 Elsevier Ltd. All rights reserved.)

The photochemical conversion of NO 2 to HONO on humic acids (HA) in the presence of benzophenone (BP) was investigated using a flow tube reactor coupled to a NO x analyzer at ambient pressure. BP significantly enhanced the reduction of NO 2 to HONO on HA under simulated sunlight, as shown by the increase of NO 2 uptake coefficient (γ) and HONO yield with the mass ratio of BP to HA. The γ and HONO yield on the mixtures of HA and BP obviously depended on the environmental conditions. Both γ and HONO yield increased with the increase of irradiation intensity and temperature, whereas they decreased with pH. The γ exhibited a negative dependence on the NO 2 concentration, which had slight influences on the HONO yield. There were maximum values for the γ and HONO yield at relative humidity (RH) of 22%. Finally, atmospheric implications about the photochemical reaction of NO 2 and HA in the presence of photosensitive species were discussed., (Copyright © 2017 Elsevier Ltd. All rights reserved.)