Observation-Based Diagnostics of Reactive Nitrogen Recycling through HONO Heterogenous Production: Divergent Implications for Ozone Production and Emission Control.

Understanding of nitrous acid (HONO) production is crucial to photochemical studies, especially in polluted environments like eastern China. In-situ measurements of gaseous and particulate compositions were conducted at a rural coastal site during the 2018 spring Ozone Photochemistry and Export from China Experiment (OPECE). This data set was applied to investigate the recycling of reactive nitrogen through daytime heterogeneous HONO production. Although HONO levels increase during agricultural burning, analysis of the observation data does not indicate more efficient HONO production by agricultural burning aerosols than other anthropogenic aerosols. Box and 1-D modeling analyses reveal the intrinsic relationships between nitrogen dioxide (NO2), particulate nitrate (pNO3), and nitric acid (HNO3), resulting in comparable agreement between observed and simulated HONO concentrations with any one of the three heterogeneous HONO production mechanisms, photosensitized NO2 conversion on aerosols, photolysis of pNO3, and conversion from HNO3. This finding underscores the uncertainties in the mechanistic understanding and quantitative parametrizations of daytime heterogeneous HONO production pathways. Furthermore, the implications for reactive nitrogen recycling, ozone (O3) production, and O3 control strategies vary greatly depending on the HONO production mechanism. On a regional scale, the conversion of HONO from pNO3 can drastically enhance O3 production, while the conversion from NO2 can reduce O3 sensitivity to NOx changes in polluted eastern China.

Decreasing Production and Potential Urban Explosion of Nighttime Nitrate Radicals amid Emission Reduction Efforts.

Nighttime oxidation by nitrate (NO3) radicals has important ramifications on nocturnal aerosol formation and hence the climate and human health. Nitrate radicals are produced by the reaction of NO2 and O3. Despite large decreases in anthropogenic emissions of nitrogen oxides (NOx = NO + NO2), a previous study found significant increases in NO3 production (PNO3) from 2014 to 2019 in China, in contrast to decreasing trends in the U.S. and Europe. Using the summer observations from 2014 to 2022, we analyze the interannual variability of nocturnal PNO3 using a systematic framework, in which PNO3 is diagnosed as a function of odd oxygen (Ox = O3 + NO2) and the NO2/O3 ratio. We did not find an increase of PNO3 from 2014 to 2022 in China due to a continuous decrease in the NO2/O3 ratio, although PNO3 is modulated by the variation in Ox. Using in situ observations obtained in Beijing in 2007, we demonstrate the potential for an upsurge resembling an "explosion" in urban nighttime NO3 radicals amid emission reduction efforts.

Global Emissions of Hydrogen Chloride and Particulate Chloride from Continental Sources.

Gaseous and particulate chlorine species play an important role in modulating tropospheric oxidation capacity, aerosol water uptake, visibility degradation, and human health. The lack of recent global continental chlorine emissions has hindered modeling studies of the role of chlorine in the atmosphere. Here, we develop a comprehensive global emission inventory of gaseous HCl and particulate Cl- (pCl), including 35 sources categorized in six source sectors based on published up-to-date activity data and emission factors. These emissions are gridded at a spatial resolution of 0.1° × 0.1° for the years 1960 to 2014. The estimated emissions of HCl and pCl in 2014 are 2354 (1661-3201) and 2321 (930-3264) Gg Cl a-1, respectively. Emissions of HCl are mostly from open waste burning (38%), open biomass burning (19%), energy (19%), and residential (13%) sectors, and the major sources classified by fuel type are combustion of waste (43%), biomass (32%), and coal (25%). Emissions of pCl are mostly from biofuel (29%) and open biomass burning processes (44%). The sectoral and spatial distributions of HCl and pCl emissions are very heterogeneous along the study period, and the temporal trends are mainly driven by the changes in emission factors, energy intensity, economy, and population.

Airborne Emission Rate Measurements Validate Remote Sensing Observations and Emission Inventories of Western U.S. Wildfires.

Carbonaceous emissions from wildfires are a dynamic mixture of gases and particles that have important impacts on air quality and climate. Emissions that feed atmospheric models are estimated using burned area and fire radiative power (FRP) methods that rely on satellite products. These approaches show wide variability and have large uncertainties, and their accuracy is challenging to evaluate due to limited aircraft and ground measurements. Here, we present a novel method to estimate fire plume-integrated total carbon and speciated emission rates using a unique combination of lidar remote sensing aerosol extinction profiles and in situ measured carbon constituents. We show strong agreement between these aircraft-derived emission rates of total carbon and a detailed burned area-based inventory that distributes carbon emissions in time using Geostationary Operational Environmental Satellite FRP observations (Fuel2Fire inventory, slope = 1.33 ± 0.04, r2 = 0.93, and RMSE = 0.27). Other more commonly used inventories strongly correlate with aircraft-derived emissions but have wide-ranging over- and under-predictions. A strong correlation is found between carbon monoxide emissions estimated in situ with those derived from the TROPOspheric Monitoring Instrument (TROPOMI) for five wildfires with coincident sampling windows (slope = 0.99 ± 0.18; bias = 28.5%). Smoke emission coefficients (g MJ-1) enable direct estimations of primary gas and aerosol emissions from satellite FRP observations, and we derive these values for many compounds emitted by temperate forest fuels, including several previously unreported species.

Chemical Production of Oxygenated Volatile Organic Compounds Strongly Enhances Boundary-Layer Oxidation Chemistry and Ozone Production.

Photolysis of oxygenated volatile organic compounds (OVOCs) produces a primary source of free radicals, including OH and inorganic and organic peroxy radicals (HO2 and RO2), consequently increasing photochemical ozone production. The amplification of radical cycling through OVOC photolysis provides an important positive feedback mechanism to accelerate ozone production. The large production of OVOCs near the surface helps promote photochemistry in the whole boundary layer. This amplifier effect is most significant in regions with high nitrogen oxides (NOx) and VOC concentrations such as Wangdu, China. Using a 1-D model with comprehensive observations at Wangdu and the Master Chemical Mechanism (MCM), we find that OVOC photolysis is the largest free-radical source in the boundary layer (46%). The condensed chemistry mechanism we used severely underestimates the OVOC amplifier effect in the boundary layer, resulting in a lower ozone production rate sensitivity to NOx emissions. Due to this underestimation, the model-simulated threshold NOx emission value, below which ozone production decreases with NOx emission decrease, is biased low by 24%. The underestimated OVOC amplifier effect in a condensed mechanism implies a low bias in the current 3-D model-estimated efficacy of NOx emission reduction on controlling ozone in polluted urban and suburban regions of China.

No Evidence for a Significant Impact of Heterogeneous Chemistry on Radical Concentrations in the North China Plain in 2014.

The oxidation of nitric oxide to nitrogen dioxide by hydroperoxy (HO2) and organic peroxy radicals (RO2) is responsible for the chemical net ozone production in the troposphere and for the regeneration of hydroxyl radicals, the most important oxidant in the atmosphere. In Summer 2014, a field campaign was conducted in the North China Plain, where increasingly severe ozone pollution has been experienced in the last years. Chemical conditions in the campaign were representative for this area. Radical and trace gas concentrations were measured, allowing for calculating the turnover rates of gas-phase radical reactions. Therefore, the importance of heterogeneous HO2 uptake on aerosol could be experimentally determined. HO2 uptake could have suppressed ozone formation at that time because of the competition with gas-phase reactions that produce ozone. The successful reduction of the aerosol load in the North China Plain in the last years could have led to a significant decrease of HO2 loss on particles, so that ozone-forming reactions could have gained importance in the last years. However, the analysis of the measured radical budget in this campaign shows that HO2 aerosol uptake did not impact radical chemistry for chemical conditions in 2014. Therefore, reduced HO2 uptake on aerosol since then is likely not the reason for the increasing number of ozone pollution events in the North China Plain, contradicting conclusions made from model calculations reported in the literature.