Reactive aldehyde chemistry explains the missing source of hydroxyl radicals.

Hydroxyl radicals (OH) determine the tropospheric self-cleansing capacity, thus regulating air quality and climate. However, the state-of-the-art mechanisms still underestimate OH at low nitrogen oxide and high volatile organic compound regimes even considering the latest isoprene chemistry. Here we propose that the reactive aldehyde chemistry, especially the autoxidation of carbonyl organic peroxy radicals (R(CO)O2) derived from higher aldehydes, is a noteworthy OH regeneration mechanism that overwhelms the contribution of the isoprene autoxidation, the latter has been proved to largely contribute to the missing OH source under high isoprene condition. As diagnosed by the quantum chemical calculations, the R(CO)O2 radicals undergo fast H-migration to produce unsaturated hydroperoxyl-carbonyls that generate OH through rapid photolysis. This chemistry could explain almost all unknown OH sources in areas rich in both natural and anthropogenic emissions in the warm seasons, and may increasingly impact the global self-cleansing capacity in a future low nitrogen oxide society under carbon neutrality scenarios.

Analysis of China's PM2.5 and ozone coordinated control strategy based on the observation data from 2015 to 2020.

The coordinated control of PM2.5 and ozone has become the strategic goal of national air pollution control. Considering the gradual decline in PM2.5 concentration and the aggravation of ozone pollution, a better understanding of the coordinated control of PM2.5 and ozone is urgently needed. Here, we collected and sorted air pollutant data for 337 cities from 2015 to 2020 to explore the characteristics of PM2.5 and ozone pollution based on China's five major air pollution regions. The results show that it is necessary to continue to strengthen the emission reduction in PM2.5 and ozone precursors, and control NOx and VOCs while promoting a dramatic emission reduction in PM2.5. The primary method of curbing ozone pollution is to strengthen the emission control of VOCs, with a long-term strategy of achieving substantial emission reductions in NOx, because VOCs and NOx are also precursors to PM2.5; hence, their reductions also contribute to the reduction in PM2.5. Therefore, the implementation of a multipollutant emission reduction control strategy aimed at the prevention and control of PM2.5 and ozone pollution is the only means to realize the coordinated control of PM2.5 and ozone.

Impact of aerosol in-situ peroxide formations induced by metal complexes on atmospheric H2O2 budgets.

Hydrogen peroxide (H2O2), hydroxyl radicals (OH), hydroperoxyl (HO2), and superoxide (O2-) radicals interacting with aerosol particles significantly affect the atmospheric pollutant budgets. A multiphase chemical kinetic box model (PKU-MARK), including the multiphase processes of transition metal ions (TMI) and their organic complexes (TMI-OrC), was built to numerically drive H2O2 chemical behaviors in the aerosol particle liquid phase using observational data obtained from a field campaign in rural China. Instead of relying on fixed uptake coefficient values, a thorough simulation of multiphase H2O2 chemistry was performed. In the aerosol liquid phase, light-driven TMI-OrC reactions promote OH, HO2/O2-, and H2O2 recycling and spontaneous regenerations. The in-situ generated aerosol H2O2 would offset gas-phase H2O2 molecular transfer into the aerosol bulk phase and promote the gas-phase level. When combined with the multiphase loss and in-situ aerosol generation involving TMI-OrC mechanism, the HULIS-Mode significantly improves the consistency between modeled and measured gas-phase H2O2 levels. Aerosol liquid phase could be a pivotal potential source of aqueous H2O2 and influence the multiphase budgets. Our work highlights the intricate and significant effects of aerosol TMI and TMI-OrC interactions on the multiphase partitioning of H2O2 when assessing atmospheric oxidant capacity.

Validating HONO as an Intermediate Tracer of the External Cycling of Reactive Nitrogen in the Background Atmosphere.

In the urban atmosphere, nitrogen oxide (NOx═NO + NO2)-related reactions dominate the formation of nitrous acid (HONO). Here, we validated an external cycling route of HONO and NOx, i.e., formation of HONO resulting from precursors other than NOx, in the background atmosphere. A chemical budget closure experiment of HONO and NOx was conducted at a background site on the Tibetan Plateau and provided direct evidence of the external cycling. An external daytime HONO source of 100 pptv h-1 was determined. Both soil emissions and photolysis of nitrate on ambient surfaces constituted likely candidate mechanisms characterizing this external source. The external source dominated the chemical production of NOx with HONO as an intermediate tracer. The OH production was doubled as a result of the external cycling. A high HONO/NOx ratio (0.31 ± 0.06) during the daytime was deduced as a sufficient condition for the external cycling. Literature review suggested the prevalence of high HONO/NOx ratios in various background environments, e.g., polar regions, pristine mountains, and forests. Our analysis validates the prevalence of external cycling in general background atmosphere and highlights the promotional role of external cycling regarding the atmospheric oxidative capacity.

A review of gas-phase chemical mechanisms commonly used in atmospheric chemistry modelling.

The atmospheric chemical mechanism is an essential component of airshed models used for investigating the chemical behaviors and impacts of species. Since the first tropospheric chemical mechanism was proposed in the 1960s, various mechanisms including Master Chemical Mechanism (MCM), Carbon Bond Mechanism (CBM), Statewide Air Pollution Research Center (SAPRC) and Regional Atmospheric Chemistry Mechanism (RACM) have been developed for different research purposes. This work summarizes the development and applications of these mechanisms, introduces their compositions and lumping methods, and compares the ways the mechanisms treat radicals with box model simulations. CBM can reproduce urban pollution events with relatively low cost compared to SAPRC and RACM, whereas the chemical behaviors of radicals and the photochemical production of ozone are described in detail in RACM. The photolysis rates of some oxygenated compounds are low in SAPRC07, which may result in underestimation of radical levels. As an explicit chemical mechanism, MCM describes the chemical processes of primary pollutants and their oxidation products in detail. MCM can be used to investigate certain chemical processes; however, due to its large size, it is rarely used in regional model simulations. A box model case study showed that the chemical behavior of OH and HO2 radicals and the production of ozone were well described by all mechanisms. CBM and SAPRC underestimated the radical levels for different chemical treatments, leading to low ozone production values in both cases. MCM and RACM are widely used in box model studies, while CBM and SAPRC are often selected in regional simulations.

Impacts of synoptic circulation on surface ozone pollution in a coastal eco-city in Southeastern China during 2014-2019.

The coastal eco-city of Fuzhou in Southeastern China has experienced severe ozone (O3) episodes at times in recent years. In this study, three typical synoptic circulations types (CTs) that influenced more than 80% of O3 polluted days in Fuzhou during 2014-2019 were identified using a subjective approach. The characteristics of meteorological conditions linked to photochemical formation and transport of O3 under the three CTs were summarized. Comprehensive Air Quality Model with extensions was applied to simulate O3 episodes and to quantify O3 sources from different regions in Fuzhou. When Fuzhou was located to the west of a high-pressure system (classified as "East-ridge"), more warm southwesterly currents flowed to Fuzhou, and the effects of cross-regional transport from Guangdong province and high local production promoted the occurrence of O3 episodes. Under a uniform pressure field with a low-pressure system occurring to the east of Fuzhou (defined as "East-low"), stagnant weather conditions caused the strongest local production of O3 in the atmospheric boundary layer. Controlled by high-pressure systems over the mainland (categorized as "Inland-high"), northerly airflows enhanced the contribution of cross-regional transport to O3 in Fuzhou. The abnormal increases of the "East-ridge" and "Inland-high" were closely related to O3 pollution in Fuzhou in April and May 2018, resulting in the annual maximum number of O3 polluted days during recent years. Furthermore, the rising number of autumn O3 episodes in 2017-2019 was mainly related to the "Inland-high", indicating the aggravation of cross-regional transport and highlighting the necessity of enhanced regional collaboration and efforts in combating O3 pollution.

Observation and modeling of organic nitrates on a suburban site in southwest China.

Here we report the measurements of two types of organic nitrates (ONs), peroxy nitrates (PNs) and alkyl nitrates (ANs), in Chengdu, China, during summer 2019. The average concentrations of PNs and ANs were 1.3 ± 1.1 ppbv and 0.5 ± 0.3 ppbv during the day, with peaks of 7.7 ppbv and 1.9 ppbv, respectively, which were in the middle and upper end of the reported levels in China. Much higher PNs and ANs concentrations were found during the photochemical pollution period than during the clean period. Box model simulation was capable of reproducing PNs during photochemical pollution episodes but showed overestimation in other periods, which was likely caused by the simplification of PNs sinks. The OH oxidation of aldehydes and ketones was the most important source of the PNs precursors, PAs (peroxyacyl radicals), except for the thermal decomposition of PNs, which was further confirmed by the relative incremental reactivity (RIR) analysis. The model basically reproduced the observed ANs by the refinement of related mechanisms, with isoprene contributing to its formation by 29.2 %. The observed PNs and total oxidants (Ox = NO2 + O3) showed a good positive correlation, with a ratio of PNs to Ox of 0.079, indicating a strong suppression of PNs chemistry to ozone formation. The model quantified the suppression of PNs chemistry on the peak ozone production rate by 21.3 % on average and inhibited ozone formation up to 20 ppbv in total. The RIR analysis suggests that the production of both O3 and ANs was in the VOC-limited regime and highlights the importance of VOC control (especially aromatics) to mitigate photochemical pollution in Chengdu. The study deepens the understanding of photochemical pollution in urban areas of western China and further emphasizes the impacts of ONs chemistry on ozone pollution.

Anthropogenic monoterpenes aggravating ozone pollution.

Monoterpenes have been known to have a critical influence on air quality and climate change through their impact on the formation of fine particles. Here we present field evidence that monoterpene oxidations largely enhanced local ozone production in a regional site in eastern China. The observed monoterpene was most likely from biomass burning rather than biogenic emissions, as indicated by the high correlation with CO at night-time, and the observed ratio of these two species was consistent with previously determined values from biomass burning experiments. Fast monoterpene oxidations were determined experimentally based on direct radical measurements, leading to a daily ozone enhancement of 4-18 parts per billion by volume (ppb), which was 6%-16% of the total ozone production, depending on the speciation of monoterpenes. It demonstrates that the previously overlooked anthropogenic monoterpenes make an important contribution to O3 production in eastern China. The role could possibly be important at similar locations across China and other parts of the world that are characterized by massive emissions, especially where there are high NO x levels. Our results highlight that anthropogenic monoterpenes should be taken into account when proceeding with the coordinated mitigation of O3 and particulate matter pollution.

[Characteristics of PM2.5 Pollution in Beijing During the Historical Period of the 2022 Olympic Winter Games].

Based on the dataset derived from January to March between 2015 and 2021 in Beijing, the PM2.5 pollution characteristics and its potential source regions during the historical period of the Beijing 2022 Olympic Winter Games and Paralympic Winter Games were investigated. From 2015 to 2018, both the number of severely polluted days (daily average ρ(PM2.5)>75 µg·m-3) and the average PM2.5 concentrations during severe pollution episodes decreased significantly in the period of January to March. While, neither variable has changed obviously since 2018. On average, severely polluted days occurred 23 times in each year between 2018 and 2021 during the period of January to March, and the average of ρ(PM2.5) was approximately 120.0 µg·m-3 during such polluted days. From January to March in 2015-2021, the severely polluted event with more than 5 consecutive polluted days occurred 2-3 times in each year, and the severest one lasted 8 d. During the historical period of the Beijing 2022 Olympic Winter Games, severely polluted days took place 2-9 d every year. The large quantities of fireworks during the Spring Festival maybe one of important primary sources of the PM2.5. The number of severely polluted days during the historical period of the Paralympic Winter Games ranged from 1 to 5 d, except for 2021 with 9 d owing to the frequent stagnant weather condition. The PM2.5 chemical composition was dominated by secondary species on severely polluted days during the historical period of the Beijing 2022 Olympic Winter Games and Paralympic Winter Games. Nitrate accounted for 46% of the measurable chemical components of PM2.5 during severe pollution events in 2020, which was remarkably higher than that during clean days in the same year (11%). The mass fraction of SO42- ranged from 12% to 19% in 2018-2020, indicating that the contribution of sulfate was much less, but cannot be ignored. The main potential source regions of PM2.5 in Beijing during the period concerned in this study were central and western Inner Mongolia, Hebei Province, Tianjin City, Shanxi Province, Shaanxi Province, central and western Shandong Province, and northern Henan Province.

Aqueous secondary organic aerosol formation attributed to phenols from biomass burning.

Biomass burning emits large quantities of phenols, which readily partition into the atmospheric aqueous phase and subsequently may react to produce aqueous secondary organic aerosol (aqSOA). For the first time, we quantitatively explored the influence of phenols emitted from biomass burning on aqSOA formation in the winter of Beijing. A typical haze episode associated with significant aqSOA formation was captured. During this episode, aqueous-phase processing of biomass burning promoted aqSOA formation was identified. Furthermore, high-resolution mass spectrum analysis provided molecular-level evidence of the phenolic aqSOA tracers. Estimation of aqSOA formation rate (RaqSOA) with compiled laboratory kinetic data indicated that biomass-burning phenols can efficiently produce aqSOA at midday, with RaqSOA of 0.42 µg m-3 h-1 accounting for 15 % of total aqSOA formation rate. The results highlight that aqSOA formation of phenols contributes the haze pollution. This implies the importance of regional joint control of biomass burning to mitigate the heavy haze.

Parameterization of the ambient aerosol refractive index with source appointed chemical compositions.

The refractive index of ambient aerosols is widely used in the climate model and remote sensing. Traditionally, the real part of the refractive index (RRI) of the ambient aerosol is calculated from the measured mass fraction of the main inorganic components with known refractive index, without full resolving the effects of variation in the RRI of organic components, which always contribute more than 50 % of the total aerosol mass. For the first time, the ambient aerosol RRI and the aerosol chemical components were measured concurrently at a suburban site Changping, in Beijing, China. Measurements results show that the ambient aerosol ranges between 1.57 and 1.71 with a mean value of 1.66. The mean mass fractions of organic aerosol (OA), nitrate, sulfate, ammonium, and chloride to total non-refractory aerosol loading are 43.1 %, 21.9 %, 21.6 %, 13.1 %, and 0.3 % respectively. Source appointment analysis of the organic aerosol show that the fossil fuel-related OA, cooking OA, biomass burning OA, less oxidized oxygenated OA and more oxidized OOA contributes 18.0 %, 11.2 %, 4.1 %, 39.9 %, 26.7 % to the total aerosol. A new parameterization scheme of the ambient aerosol RRI, which considers the source appointed OA, is proposed based on the concurrent measurements of RRI and chemical composition. The measured and parameterized RRI shows good consistency with a correlation coefficient of 0.79 and slope of 0.98. Our measurement results reveal that a significant deviation of the calculated RRI exists without considering the variation of the RRI of the aerosol organic component. The parametrization scheme is adopted and applicable in aerosol model for bettering estimating the corresponding optical and radiative effects.

Variations in source contributions of particle number concentration under long-term emission control in winter of urban Beijing.

Many studies revealed the rapid decline of atmospheric PM2.5 in Beijing due to the emission control measures. The variation of particle number concentration (PN) which has important influences on regional climate and human health, however, was rarely reported. This study measured the particle number size distributions (PNSD) in 3-700 nm in winter of Beijing during 2013-2019. It was found that PN decreased by 58% from 2013 to 2017, but increased by 29% from 2017 to 2019. By Positive matrix factorization (PMF) analysis, five source factors of PNSD were identified as Nucleation, Fresh traffic, Aged traffic + Diesel, Coal + biomass burning and Secondary. Overall, factors associated with primary emissions were found to decrease continuously. Coal + biomass burning dominated the reduction (65%) among the three primary sources during 2013-2017, which resulted from the great efforts on emission control of coal combustion and biomass burning. Fresh traffic and Aged traffic + Diesel decreased by 43% and 66%, respectively, from 2013 to 2019, as a result of the upgrade of the vehicle emission standards in Beijing-Tianjin-Hebei area. On the other hand, the contribution from Nucleation and Secondary decreased with the reduction of gaseous precursors in 2013-2017, but due to the increased intensity of new particle formation (NPF) and secondary oxidation, they increased by 56% and 70%, respectively, from 2017 to 2019, which led to the simultaneously increase of PN and particle volume concentration. This study indicated that NPF may play an important role in urban atmosphere under continuous air quality improvement.

Particle hygroscopicity inhomogeneity and its impact on reactive uptake.

Atmospheric particles are important reaction vessels for multiphase chemistry. We conducted a meta-analysis of previous field observations in various environments (includes ocean, urban and rural regions), showing that particle hygroscopicity inhomogeneity (PHI) is ubiquitous for the continental atmospheric particles, in which a considerable part of the particulate matters is hydrophobic (10%-33% on average). However, the effects of PHI in quantifying the uptake process of reactive gases are still unclear. Here, taking N2O5 uptake as an example, we showed that using a laboratory-based parameterization scheme without considering the PHI might result in a misestimation of uptake rate coefficient, especially under low ambient relative humidity (RH). Such misestimation may be caused by the differences of the uptake coefficients, as well as the proportion of surface area concentration (SA) between hydrophilic and hydrophobic particles. We suggested that the PHI should be well-considered in establishing the reactive traces gases heterogeneous uptake parameterizations.

Field observations and quantifications of atmospheric formaldehyde partitioning in gaseous and particulate phases.

Formaldehyde (HCHO) can possibly be taken by atmospheric particles due to its moderate solubility. Although previous model studies have proposed that uptake by particles was a large sink for HCHO, direct observation of HCHO partitioning and estimation of HCHO uptake coefficient (γ) for tropospheric conditions are still limited. In this work, online measurements of gaseous HCHO (HCHOg) and particulate HCHO (HCHOp) were carried out simultaneously at an urban site in Beijing in winter and spring. The results indicated that the average concentrations of HCHOp ranged from 0.15 to 0.4 µg m-3, accounting for 1.2% to 10% of the total HCHO (i.e., HCHOg + HCHOp). The median values of estimated γ based on the measured data were in the range of about 1.09 ∗ 10-5-2.42 ∗ 10-4, with lower values during PM2.5 pollution episodes. Besides, the pH and liquid water content of aerosols that are mainly determined by ambient relative humidity (RH) and inorganic salt composition were identified as the main influencing factors of γ. We propose that the HCHO uptake process was mainly driven by hydrone and hydrogen ions in particles.

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.

Direct evidence of local photochemical production driven ozone episode in Beijing: A case study.

We present a comprehensive field campaign conducted in Beijing, September 2016, to elucidate the photochemical smog pollution, i.e. Ozone (O3). The observed daily maximum hydroxyl radical (OH) and hydroperoxy radical (HO2) concentrations were up to 1 × 107 cm-3 and 6 × 108 cm-3, respectively, indicating the active photochemistry in autumn Beijing. Photolysis of nitrous acid (HONO) and O3 contributed 1-2 ppbv h-1 to OH primary production during daytime. OH termination were dominated by the reaction with nitric oxide (NO) and nitrogen dioxide (NO2), which were in general larger than primary production rates, indicating other primary radical sources maybe important. The measurement of radicals facilitates the direct determination of local ozone production rate P (Ox) (Ox = O3 + NO2). The integrated P(Ox) reached 75 ppbv in afternoon (for 4 h) when planetary boundary layer was well developed. At the same time period, the observed total oxidant concentrations Ox, increased significantly by 70 ppbv. In addition, the Ox measurement showed compact increase in 12 stations both temporally and spatially in Beijing, indicating that active photochemical production happened homogenously throughout the city. The back-trajectory analysis showed that Beijing was isolated from the other cities during the episode, which further proved that the fast ozone pollution was contributed by local photochemical production rather than regional advection.

Characteristics and sources of volatile organic compounds during pollution episodes and clean periods in the Beijing-Tianjin-Hebei region.

Volatile organic compounds (VOCs) play an important role in air pollution. In this study, we conducted comprehensive field observations to investigate wintertime air pollution in Beijing, Wangdu, and Dezhou in the Beijing-Tianjin-Hebei region during 2017 and 2018. The average VOC concentrations of the three sites were 35.6 ± 26.6, 70.9 ± 56.3, and 50.5 ± 40.0 ppbv, respectively. The species with the highest concentration were similar in all three sites and included ethane, ethylene, acetylene, acetone, and toluene. The VOC mixing ratios of the three sites showed synchronous growth during pollution episodes and were 1.2-2 times higher than those during clean periods. Moreover, the OH loss rates (LOH) during pollution episodes were 1.2-1.7 times that during clean periods. The crucial reactive species in the three sites were ethylene, propylene, and acetaldehyde, contributing approximately 70% to the total LOH during pollution periods. According to the source apportionment analysis, vehicle exhausts were the largest source of VOCs in Beijing, accounting for more than 50% of the total emissions. During the pollution episodes, Beijing's industrial emissions decreased, but the secondary and background sources increased. Coal combustion was significant (approximately 40%) in Wangdu and should therefore be prioritized in emission reduction policies. In Dezhou, industrial emissions had a considerable impact on the VOC mixing ratio during pollution periods and should therefore be prioritized. The backward trajectory analysis showed that VOCs from the southern region likely contribute to Beijing's VOC pollution, highlighting the importance of regional integration for air quality management.

Secondary aerosol formation from a Chinese gasoline vehicle: Impacts of fuel (E10, gasoline) and driving conditions (idling, cruising).

Chassis dynamometer experiments were conducted to investigate the effect of vehicle speed and usage of ethanol-blended gasoline (E10) on formation and evolution of gasoline vehicular secondary organic aerosol (SOA) using a Gothenburg Potential Aerosol Mass (Go: PAM) reactor. The SOA forms rapidly, and its concentration exceeds that of primary organic aerosol (POA) at an equivalent photochemical age (EPA) of ~1 day. The particle effective densities grow from 0.62 ± 0.02 g cm-3 to 1.43 ± 0.07 g cm-3 with increased hydroxyl radical (OH) exposure. The maximum SOA production under idling conditions (4259-7394 mg kg-fuel-1) is ~20 times greater than under cruising conditions. There was no statistical difference between SOA formation from pure gasoline and its formation from E10. The slopes in Van Krevelen diagram indicate that the formation pathways of bulk SOA includes the addition of both alcohol/peroxide functional groups and carboxylic acid formation from fragmentation. A closure estimation of SOA based on bottom-up and top-down methods shows that only 16%-38% of the measured SOA can be explained by the oxidation of measured volatile organic compounds (VOCs), suggesting the existence of missing precursors, e.g. unmeasured VOCs and probably semivolatile or intermediate volatile organic compounds (S/IVOCs). Our results suggest that applying parameters obtained from unified driving cycles to model SOA concentrations may lead to large discrepancies between modeled and ambient vehicular SOA. No reduction in vehicular `SOA production is realized by replacing normal gasoline with E10.

Characterizing nitrate radical budget trends in Beijing during 2013-2019.

Nitrate (NO3) radical is an important oxidant in the atmosphere as it regulates the NOx budget and impacts secondary pollutant formation. Here, a long-term observational dataset of NO3-related species at an urban site in Beijing was used to investigate changes in the NO3 budget and their atmospheric impacts during 2013-2019, in this period the Clean Air Actions Plan was carried out in China. We found that (1) changes in NO3 precursors (NO2 and O3) led to a significant increase in NO3 formation in the surface layer in winter but a decrease in summer; (2) a reduction in NOx promoted thermal equilibrium, favoring the formation of NO3 rather than dinitrogen pentoxide (N2O5). The simultaneous decrease in PM2.5, during these years, further weakened the N2O5 heterogeneous uptake; (3) a box model simulation revealed that both the reactions of NO3 with volatile organic compounds (VOC) and N2O5 uptake were weakened in summer, implying that the policy actions implemented help to moderate secondary aerosol formation caused by NO3 and N2O5 chemistry in summer; and (4) during winter, both NO3 + VOC and N2O5 uptake were enhanced. Specifically, for the N2O5 uptake, the rapid increase in NO3 production, or to some extent, NO3 oxidation capacity, far outweighed the negative shift effect, leading to a net enhancement of N2O5 uptake in winter, which indicates that the action policy implemented led to an adverse effect on particulate nitrate formation via N2O5 uptake in winter. This may explain the persistent winter particulate nitrate pollution in recent years. Our results highlight the systematic changes in the NO3 budget between 2013 and 2019 in Beijing, which subsequently affect secondary aerosol formation in different seasons.