Nitrate is an increasingly important component of fine particulate matter (PM2.5) during winter in northern China. Past emission control has been ineffective in reducing winter nitrate. Here, we use extensive observations and a model with state-of-the-art nitrogen chemistry to identify the key factors that control the nitrate formation in the heavily polluted North China Plain (NCP). In contrast to the previous view of weak winter photochemistry, we show that the O3 and OH productions are sufficiently high in winter to facilitate fast gas-phase and heterogeneous conversion of NOX to nitrate over the NCP. Increasing O3 and OH productions from higher precursor levels and fast ROX cycling accelerate the nitrate generation during heavy pollution. We find that the 31.8% reduction of NOX emissions from 2010 to 2017 in the NCP lowers surface nitrate by only 0.2% and even increases nitrate in some polluted areas. This is mainly due to the increase of O3 and OH (by ∼30%), which has subsequently increased the conversion efficiency of NOX to HNO3 (by 38.7%). Future control strategies for the winter haze should also aim to lower photochemical oxidants, via larger and synchronized NOX and VOCs emissions reduction, to overcome the effects of nonlinear photochemistry and aerosol chemical feedback.

Persistent Heavy Winter Nitrate Pollution Driven by Increased Photochemical Oxidants in Northern China.

Increasing importance of nitrate formation for heavy aerosol pollution in two megacities in Sichuan Basin, southwest China.

Regional differences in spatial spillover and hysteresis effects: A theoretical and empirical study of environmental regulations on haze pollution in China

The unprecedented slowdown in China during the COVID-19 period of November 2019 to April 2020 should have reduced pollution in smog-laden cities. However, moderate resolution imaging spectrometer (MODIS) satellite retrievals of aerosol optical depth (AOD) show a marked increase in aerosols over the Beijing–Tianjin–Hebei (BHT) region and most of Northeast and Central China, compared with the previous winter. Fine particulate (PM2.5) data from ground monitoring stations show an increase of 19.5% in Beijing during January and February 2020, and no reduction for Tianjin. In March and April 2020, a different spatial pattern emerges, with very high AOD levels observed over 50% of the Chinese mainland, and including peripheral regions in the northwest and southwest. At the same time, ozone monitoring instrument (OMI) satellite-derived NO2 concentrations fell drastically across China. The increase in PM2.5 while NO2 decreased in BTH and across China is likely due to enhanced production of secondary particulates. These are formed when reductions in NOx result in increased ozone formation, thus increasing the oxidizing capacity of the atmosphere. Support for this explanation is provided by ground level air quality data showing increased volume of fine mode aerosols throughout February and March 2020, and increased levels of PM2.5, relative humidity (RH), and ozone during haze episodes in the COVID-19 lockdown period. Backward trajectories show the origin of air masses affecting industrial centers of North and East China to be local. Other contributors to increased atmospheric particulates may include inflated industrial production in peripheral regions to compensate loss in the main population and industrial centers, and low wind speeds. Satellite monitoring of the extraordinary atmospheric conditions resulting from the COVID-19 shutdown could enhance understanding of smog formation and attempts to control it.

Air pollution scenario over China during COVID-19

Evidence for superiority of conventional adsorbents in the sorptive removal of gaseous benzene under real-world conditions: Test of activated carbon against novel metal-organic frameworks

Secondary inorganic aerosols formation during haze episodes at an urban site in Beijing, China

To understand the characteristics of winter fine aerosol pollution in Beijing, we conducted continuous measurements of the atmospheric trace gas ammonia (NH3), PM2.5, and inorganic ions in PM2.5 at an urban site in Beijing from February 13 to March 17, 2015. The hourly average concentration of NH3 throughout the campaign was 15.4 ± 17.5 ppb. NH3 concentrations correlated well with NH4+ in PM2.5, indicating the dominant precursor role of NH3 on NH4+ formation. The diurnal profile indicated an increase in NH3 concentrations during the morning rush hours, which was likely due to vehicle emissions. The mean ammonium conversion ratio (NHR) was 0.26, with the highest value of 0.32 in the afternoon. Elevated NHR, nitrate oxidation ratio (NOR), and NH4+ coincided with the significant increase in O3 levels in the afternoon, indicating the large daytime formation of NH4NO3 via photochemical reactions. Moreover, higher NHR values occurred under higher relative humidity (RH >60%) and lower temperature (0–10 °C). NHR increased during the nighttime and correlated well with RH, indicating the dominant role of heterogeneous reactions on gas-particle partitioning. The sulfate oxidation ratio (SOR) and NOR showed positive correlations with RH, which suggests that the conversions of SO2 to SO42− and NO2 to NO3− were sensitive to changes in RH. The sustained increase in SO42− concentrations at RH >60% suggests that RH had a higher influence on SO42− formation than on NO3− formation. As the sole precursor of NH4+, NH3 significantly enhanced daytime NH4NO3 formation via homogeneous gas-phase reactions and also promoted sulfate formation via both homogeneous and heterogeneous reactions. Moreover, the back trajectory results inferred a high contribution of southwestern air masses to atmospheric NH3 and NH4+ aerosol variations in Beijing. The result suggests the need for controlling the vehicle emissions to reduce the high levels of NH3 and alleviate PM2.5 pollution in winter in Beijing.

Characteristics of ambient ammonia and its effects on particulate ammonium in winter of urban Beijing, China

Vapor processing device is a device that can control the headspace pressure in the underground storage tanks and recover the vapor. By analyzing the chemical composition of volatile organic compounds (VOCs) at the inlet and outlet of the vapor processing device, the ozone formation potential (OFP) and secondary organic aerosol formation potential (SOAP) were estimated by maximum incremental reaction (MIR) and fractional aerosol coefficients (FAC), and the secondary pollution formation contribution of VOCs were quantitatively evaluated. The results showed that:① the ρ(total volatile organic compounds, TVOC) at the inlet and outlet of the vapor processing device were 436-706 g·m-3 and 4.98-10.04 g·m-3, respectively. Alkanes (72%±4%), oxygenated organics (14%±2%), and olefins (11%±5%) were the dominant components of VOCs emissions. There were little differences in VOCs emissions from the different vapor processing devices; the key species were i-pentane (approximately 25%), followed by n-butane, i-butane, and n-pentane. ② The ozone source reactivity (SR) of VOCs emissions from the outlet of the vapor processing device was 2.6-3.3 g·g-1, and the OFP was 3.5-25.6 g·m-3. Olefins contributed the most (43%-69%), followed by alkanes (20%-35%) and oxygenated organics (10%-22%). Butene, cis-2-butene, trans-2-butene, i-pentane, and propionaldehyde were the species that highly contributed to OFP. ③ Aromatics in VOCs emissions contributed the most to SOAP (80%-92%), and the main active species were toluene, 1, 2, 4-trimethylbenzene, 1, 3, 5-trimethylbenzene, and p-diethylbenzene. The research showed that different VOCs species emitted by the vapor processing device contributed obvious differences to the secondary atmospheric pollution, and butene species and aromatics such as toluene were the focus of VOCs emission control of vehicle gasoline and vapor processing device.

Yuhu Huang

Papers

Secondary inorganic aerosols formation during haze episodes at an urban site in Beijing, China

Characteristics of ambient ammonia and its effects on particulate ammonium in winter of urban Beijing, China

[Chemical Composition of VOCs from Service Stations Vapor Processing Device and Associated Contributions to Secondary Pollution].

Emission of VOCs from service stations in Beijing: Species characteristics and pollutants co-control based on SOA and O3.