Impact of Molecular Chlorine Production from Aerosol Iron Photochemistry on Atmospheric Oxidative Capacity in North China.

Elevated levels of atmospheric molecular chlorine (Cl2) have been observed during the daytime in recent field studies in China but could not be explained by the current chlorine chemistry mechanisms in models. Here, we propose a Cl2 formation mechanism initiated by aerosol iron photochemistry to explain daytime Cl2 formation. We implement this mechanism into the GEOS-Chem chemical transport model and investigate its impacts on the atmospheric composition in wintertime North China where high levels of Cl2 as well as aerosol chloride and iron were observed. The new mechanism accounts for more than 90% of surface air Cl2 production in North China and consequently increases the surface air Cl2 abundances by an order of magnitude, improving the model's agreement with observed Cl2. The presence of high Cl2 significantly alters the oxidative capacity of the atmosphere, with a factor of 20-40 increase in the chlorine radical concentration and a 20-40% increase in the hydroxyl radical concentration in regions with high aerosol chloride and iron loadings. This results in an increase in surface air ozone by about 10%. This new Cl2 formation mechanism will improve the model simulation capability for reactive chlorine abundances in the regions with high emissions of chlorine and iron.

Identifying Driving Factors of Atmospheric N2O5 with Machine Learning.

Dinitrogen pentoxide (N2O5) plays an essential role in tropospheric chemistry, serving as a nocturnal reservoir of reactive nitrogen and significantly promoting nitrate formations. However, identifying key environmental drivers of N2O5 formation remains challenging using traditional statistical methods, impeding effective emission control measures to mitigate NOx-induced air pollution. Here, we adopted machine learning assisted by steady-state analysis to elucidate the driving factors of N2O5 before and during the 2022 Winter Olympics (WO) in Beijing. Higher N2O5 concentrations were observed during the WO period compared to the Pre-Winter-Olympics (Pre-WO) period. The machine learning model accurately reproduced ambient N2O5 concentrations and showed that ozone (O3), nitrogen dioxide (NO2), and relative humidity (RH) were the most important driving factors of N2O5. Compared to the Pre-WO period, the variation in trace gases (i.e., NO2 and O3) along with the reduced N2O5 uptake coefficient was the main reason for higher N2O5 levels during the WO period. By predicting N2O5 under various control scenarios of NOx and calculating the nitrate formation potential from N2O5 uptake, we found that the progressive reduction of nitrogen oxides initially increases the nitrate formation potential before further decreasing it. The threshold of NOx was approximately 13 ppbv, below which NOx reduction effectively reduced the level of night-time nitrate formations. These results demonstrate the capacity of machine learning to provide insights into understanding atmospheric nitrogen chemistry and highlight the necessity of more stringent emission control of NOx to mitigate haze pollution.

Reactive Chlorine Species Advancing the Atmospheric Oxidation Capacities of Inland Urban Environments.

Chlorine (Cl) radicals from photolabile chlorine species are highly reactive and can affect the fate of air pollutants in the atmosphere. Although several campaigns have been conducted, typically in coastal environments, long-term observations of reactive chlorine species and their impacts on atmospheric oxidation capacities (AOCs) are lacking. Here, we report nearly full-year observations of Cl2 and ClNO2 levels in Beijing and evaluate their impacts on the AOC with a box model coupled with Cl chemistry. Cl radicals promote the circulation of OH-HO2-RO2 by accelerating the OH chain lengths by up to 12.6% on average, hence boosting the AOC, especially in the winter or spring. This promotion effect is nonlinearly dependent on the VOC and NOx concentrations, thus leading to a slight shift in ozone formation from a VOC-sensitive regime to a transition regime with seasonal differences. Given the ubiquitous reactive chlorines in polluted inland urban regions, the AOCs and the formation of secondary pollutants will be underestimated if the reactive chlorine species are neglected.

Molecular Characterization of Oxygenated Organic Molecules and Their Dominating Roles in Particle Growth in Hong Kong.

Oxygenated organic molecules (OOMs) are critical intermediates linking volatile organic compound oxidation and secondary organic aerosol (SOA) formation. Yet, the understanding of OOM components, formation mechanism, and impacts are still limited, especially for urbanized regions with a cocktail of anthropogenic emissions. Herein, ambient measurements of OOMs were conducted at a regional background site in South China in 2018. The molecular characteristics of OOMs revealed dominant nitrogen-containing products, and the influences of different factors on OOM composition and oxidation state were elucidated. Positive matrix factorization analysis resolved the complex OOM species to factors featured with fingerprint species from different oxidation pathways. A new method was developed to identify the key functional groups of OOMs, which successfully classified the majority species into carbonyls (8%), hydroperoxides (7%), nitrates (17%), peroxyl nitrates (10%), dinitrates (13%), aromatic ring-retaining species (6%), and terpenes (7%). The volatility estimation of OOMs was improved based on their identified functional groups and was used to simulate the aerosol growth process contributed by the condensation of those low-volatile OOMs. The results demonstrate the predominant role of OOMs in contributing sub-100 nm particle growth and SOA formation and highlight the importance of dinitrates and anthropogenic products from multistep oxidation.

Secondary Formation and Impacts of Gaseous Nitro-Phenolic Compounds in the Continental Outflow Observed at a Background Site in South China.

Nitro-phenolic compounds (NPs) have attracted increasing attention because of their health risks and impacts on visibility, climate, and atmospheric chemistry. Despite many measurements of particulate NPs, the knowledge of their gaseous abundances, sources, atmospheric fates, and impacts remains incomplete. Here, 18 gaseous NPs were continuously measured with a time-of-flight chemical ionization mass spectrometer at a background site in South China in autumn and winter. Abundant NPs were observed in the continental outflows from East Asia, with a total concentration up to 122.1 pptv. Secondary formation from the transported aromatics dominated the observed NPs, with mono-NPs exhibiting photochemical daytime peaks and nighttime enrichments of di-NPs and Cl-substituted NPs. The budget analysis indicates that besides the •OH oxidation of aromatics, the NO3• oxidation also contributed significantly to the daytime mono-NPs, while the further oxidation of mono-NPs by NO3• dominated the nocturnal formation of di-NPs. Photolysis was the main daytime sink of NPs and produced substantial HONO, which would influence atmospheric oxidation capacity in downwind and background regions. This study provides quantitative insights on the formation and impacts of gaseous NPs in the continental outflow and highlights the role of NO3• chemistry in the secondary nitro-aromatics production that may facilitate regional pollution.

Pollution-Derived Br2 Boosts Oxidation Power of the Coastal Atmosphere.

The bromine atom (Br•) has been known to destroy ozone (O3) and accelerate the deposition of toxic mercury (Hg). However, its abundance and sources outside the polar regions are not well-known. Here, we report significant levels of molecular bromine (Br2)─a producer of Br•─observed at a coastal site in Hong Kong, with an average noontime mixing ratio of 5 ppt. Given the short lifetime of Br2 (∼1 min at noon), this finding reveals a large Br2 daytime source. On the basis of laboratory and field evidence, we show that the observed daytime Br2 is generated by the photodissociation of particulate nitrate (NO3-) and that the reactive uptake of dinitrogen pentoxide (N2O5) on aerosols is an important nighttime source. Model-calculated Br• concentrations are comparable with that of the OH radical─the primary oxidant in the troposphere, accounting for 24% of the oxidation of isoprene, a 13% increase in net O3 production, and a nearly 10-fold increase in the production rate of toxic HgII. Our findings reveal that reactive bromines play a larger role in the atmospheric chemistry and air quality of polluted coastal and maritime areas than previously thought. Our results also suggest that tightening the control of emissions of two conventional pollutants (NOx and SO2)─thereby decreasing the levels of nitrate and aerosol acidity─would alleviate halogen radical production and its adverse impact on air quality.

Fast near-surface ClNO2 production and its impact on O3 formation during a heavy pollution event in South China.

Atmospheric nitryl chloride (ClNO2) acts as a reservoir of both NOx and reactive chlorine radicals and therefore affects atmospheric oxidation chemistry and the production of secondary pollutants such as ozone (O3). However, the factors contributing to ClNO2 production and its impact on O3 formation in the polluted atmosphere are not fully understood. Here, we investigated the causes and impacts of extremely high ClNO2 levels (up to 8.3 ppbv, 1 min average) in a winter pollution episode at a semi-rural surface site in South China. Anthropogenic activities (mainly coal burning) produced an abundant amount of chloride, and high NO3 production rates and efficient N2O5 uptake by aerosols facilitated ClNO2 production at night. We used a chemical box model to assess the ClNO2 impact on next-day O3 production both at the site and in downwind areas. The model results showed that ClNO2 chemistry led to 6.6 % enhancement of net Ox (=NO2 + O3) production at the site, while the enhancement was increased to 11.2 % in the air mass transporting downwind, which resulted in 20 ppbv (38.5 % max) increment of peak O3 concentration. ClNO2 also changed the response of O3 to reduction in the concentration of O3 precursors (NOx and anthropogenic volatile organic compounds (VOCs)), thereby affecting the design of NOx and VOC reduction strategies for O3 pollution mitigation. Reducing chloride emissions can help alleviate the emission reduction burden for NOx and anthropogenic VOCs.

Investigating the sources of atmospheric nitrous acid (HONO) in the megacity of Beijing, China.

Nitrous acid (HONO) can powerfully influence atmospheric photochemistry by producing hydroxyl radical (OH), which is a crucial oxidant that controls the fate of atmospheric trace species. To deduce HONO formation mechanisms in polluted regions, two field observations were conducted in urban Beijing during the early summer of 2017 and the winter of 2018. These two seasons bore distinguishing pollution characteristics with a higher degree of ageing and heavier aerosol loading in the early summer and more abundant NOx (NOx = NO + NO2) in the winter. Elevated concentrations of HONO were observed during these two seasons, with the mean ± standard deviation (maximum) concentrations of 1.25 ± 0.94 (6.69) ppbv and 1.04 ± 1.27 (9.55) ppbv in early summer and winter, respectively. The observed daytime (08:00-17:00 h, local time) HONO production rate was several times higher in early summer than in winter (4.44 ± 1.93 ppbv h-1 vs. 0.88 ± 0.49 ppbv h-1). Budget analysis revealed distinct daytime HONO formation mechanisms during these two seasons. Photo-induced heterogeneous conversion of NO2 on the ground surface dominated in early summer, and homogeneous reaction of NO + OH was dominant in winter. Photolysis of HONO was the major source of primary OH in both seasons, and thus, played a key role in the regulation of atmospheric oxidising capacity. This study demonstrates the significant seasonal variations in HONO budget and underlines the predominant role of HONO in primary OH production in Beijing. Our findings will be helpful to gain an understanding of the chemical mechanisms underlying the formation of secondary pollution in metropolitan areas.

Nitrous acid in the polluted coastal atmosphere of the South China Sea: Ship emissions, budgets, and impacts.

Nitrous acid (HONO) can significantly contribute to hydroxyl radicals (OH) and thus regulate atmospheric oxidation chemistry; however, ambient HONO sources are not well quantified and vary in different environments. In this study, we conducted comprehensive field observations at a coastal site in the South China Sea and performed chemical box modelling to demonstrate contrasting budgets and impacts of diurnal atmospheric HONO derived from the sea, coastline and continent. The ship emission ratio of HONO/nitrogen oxides (NOx) (1.21 ± 0.99%) was calculated from hundreds of night-time fresh plume measurements. Offshore marine air was frequently influenced by ship exhausts, and the sea acted as an HONO sink. Heterogeneous conversions of nitrogen dioxide (NO2) on underlying surfaces and photolysis of adsorbed nitric acid (HNO3(ads)) were the major HONO sources in coastal air, when heterogeneous NO2 conversions on the ground surface and the homogeneous NO + OH reaction dominated HONO formation in continental air. HONO photolysis was a significant source of reactive radicals (ROx = OH + HO2 + RO2) in these air masses. Atmospheric box model including only homogeneous HONO source of the NO + OH reactions significantly underpredicted the OH concentration and atmospheric oxidising capacity in coastal and continental air. This study provides new insights into the complex sources and significant impacts of HONO in the polluted coastal boundary layer.

Photodissociation of particulate nitrate as a source of daytime tropospheric Cl2.

Chlorine atoms (Cl) are highly reactive and can strongly influence the abundances of climate and air quality-relevant trace gases. Despite extensive research on molecular chlorine (Cl2), a Cl precursor, in the polar atmosphere, its sources in other regions are still poorly understood. Here we report the daytime Cl2 concentrations of up to 1 ppbv observed in a coastal area of Hong Kong, revealing a large daytime source of Cl2 (2.7 pptv s-1 at noon). Field and laboratory experiments indicate that photodissociation of particulate nitrate by sunlight under acidic conditions (pH < 3.0) can activate chloride and account for the observed daytime Cl2 production. The high Cl2 concentrations significantly increased atmospheric oxidation. Given the ubiquitous existence of chloride, nitrate, and acidic aerosols, we propose that nitrate photolysis is a significant daytime chlorine source globally. This so far unaccounted for source of chlorine can have substantial impacts on atmospheric chemistry.

An unexpected large continental source of reactive bromine and chlorine with significant impact on wintertime air quality.

Halogen atoms affect the budget of ozone and the fate of pollutants such as hydrocarbons and mercury. Yet their sources and significances in polluted continental regions are poorly understood. Here we report the observation of unprecedented levels (averaging at 60 parts per trillion) of bromine chloride (BrCl) at a mid-latitude site in North China during winter. Widespread coal burning in rural households and a photo-assisted process were the primary source of BrCl and other bromine gases. BrCl contributed about 55% of both bromine and chlorine atoms. The halogen atoms increased the abundance of 'conventional' tropospheric oxidants (OH, HO2 and RO2) by 26%-73%, and enhanced oxidation of hydrocarbon by nearly a factor of two and the net ozone production by 55%. Our study reveals the significant role of reactive halogen in winter atmospheric chemistry and the deterioration of air quality in continental regions where uncontrolled coal combustion is prevalent.

Vehicle emissions in a middle-sized city of China: Current status and future trends.

Vehicle emissions are regarded as an important contributor to urban air pollution in China and most previous studies focused on megacities. However, the vehicle pollution in middle-sized cities becomes more severe due to the increasing vehicle population (VP) and lagged control policy. This study takes Langfang, a typical middle-sized city bordered by two megacities (Beijing and Tianjin), as the target domain to investigate vehicle emissions. The speed correction curves (SCC) are introduced to improve the vehicle emission factors (EF) simulation in official technical guidelines on emission inventory (GEI). A multi-year vehicle emission inventory (from 2011 to 2025) is developed in Langfang. From 2011 to 2017, the total vehicle emissions in Langfang decrease for carbon monoxide (CO), but increase for volatile organic compounds (VOCs), nitrogen oxides (NOx), and inhalable particles (PM10), respectively. From 2018 to 2025, the emissions would increase more rapidly in Langfang than in Beijing and Tianjin, indicating the middle-sized cities may become a significant contributor to air pollution in China. Four possible control policies, including VP constrained (VPC), public transportation promotion (PTP), new energy vehicles promotion (NEP), and freight transportation structure optimization (FTO) are evaluated. The most significant emissions reductions are observed under the FTO for CO, NOx, and PM10, and under the VPC for VOCs. The spatial distributions of vehicle emissions show a high order of heterogeneity, indicating that local conditions should be considered in policy formulation in addition to national consistency. More comprehensive policies should be implemented to mitigate the vehicle pollution in middle-sized cities.

Characterization of organic aerosols and their precursors in southern China during a severe haze episode in January 2017.

The rapid industrialization and economic development in the Pearl River Delta (PRD) region of southern China have led to a substantial increase in anthropogenic emissions and hence frequent haze pollution over the past two decades. In early January 2017, a severe regional haze pollution episode was captured in the PRD region, with a peak PM2.5 concentration of around 400µgm-3, the highest value ever reported at this site. During the haze episode, elevated concentrations of oxygenated volatile organic compounds (OVOCs, 33±16 ppbv) and organic matter (41±15µg m-3) were observed, indicating the enhanced roles of secondary organic aerosols (SOAs) in the formation of haze pollution. Water-soluble organic carbon (WSOC, 12.8±5.5µg C m-3) dominated the organic aerosols, with a WSOC/OC ratio of 0.63±0.12 and high correlation (R=0.85) with estimated secondary organic carbon (SOC), suggesting the predominance of a secondary origin of the measured organic aerosols during the haze episode. Four carboxylic acids (oxalic, acetic, formic, and pyruvic acids) were characterized in the aerosols (1.30±0.38µgm-3) and accounted for 3.6±1.2% of WSOC in carbon mass, with oxalic acid as the most abundant species. The simultaneous measurements of volatile organic compounds (VOCs), OVOCs, and organic acids in aerosols at this site provided an opportunity to investigate the relationship between the precursors and the products, as well as the potential formation pathways. Water-soluble aldehydes and ketones, predominantly produced via the oxidation of anthropogenic VOCs (mainly propane, toluene, n-butane, and m, p-xylene), were the main contributors of the organic acids. The formation of OVOCs is largely attributed to gas-phase photochemical oxidation, whereas the WSOC and dicarboxylic acids were produced from both photochemistry and nocturnal heterogeneous reactions. These findings provided further insights into the oxidation and evolution of organic compounds during the haze pollution episode.

Abundance and origin of fine particulate chloride in continental China.

Particulate chloride can be converted to nitryl chloride (ClNO2) through heterogeneous reactions with dinitrogen pentoxide (N2O5), and photolysis of ClNO2 affects atmospheric oxidative capacity. However, the characteristics and sources of chloride, especially those with an anthropogenic origin, are poorly characterized, which makes it difficult to evaluate the effects of ClNO2 on radical chemistry and air quality in polluted regions. Aerosol composition data from the literature were compiled to derive the spatial distributions of particulate chloride across China, and hourly aerosol composition data collected at a highly polluted inland urban site in eastern China and at a coastal site in southern China were analysed to gain further insights into non-oceanic sources of chloride. The results show that particulate chloride is concentrated mainly in fine particles and that high chloride loadings are observed in the inland urban areas of northern and western China with higher Cl-/Na+ mass ratios (2.46 to 5.00) than sea water (1.81), indicative of significant contributions from anthropogenic sources. At the inland urban site, the fine chloride displays distinct seasonality, with higher levels in winter and summer. Correlation analysis and positive matrix factorization (PMF) results indicate that coal combustion and residential biomass burning are the main sources (84.8%) of fine chloride in winter, and open biomass burning is the major sources (52.7%) in summer. The transport of plumes from inland polluted areas leads to elevated fine chloride in coastal areas. A simulation with WRF-Chem model confirmed a minor contribution of sea-salt aerosol to fine chloride at the inland site during summer with winds from the East Sea. The widespread sources of chloride, together with abundant NOx and ozone, suggest significant ClNO2 production and subsequent enhanced photochemical processes over China.