Comparative analysis for the impacts of VOC subgroups and atmospheric oxidation capacity on O3 based on different observation-based methods at a suburban site in the North China Plain.

The persistent O3 pollution in the Beijing-Tianjin-Hebei (BTH) region remains unresolved, largely due to limited comprehension of O3-precursor relationship and photochemistry drivers. In this work, intraday O3 sensitivity evolution from VOC-limited (volatile organic compound) regime in the forenoon to transition regime in the late afternoon was inferred by relative incremental reactivity (RIR) in summer 2019 at Xianghe, a suburban site in BTH region, suggesting that VOC-focused control policy could combine with stringent afternoon NOx control. Then detailed impacts of VOC subgroups on O3 formation were further comprehensively quantified by parametric OH reactivity (KOH), O3 formation potential (OFP), as well as RIR weighted value and O3 formation path tracing (OFPT) approach based on photochemical box model. O3 episode days corresponded to stronger O3 formation, depicted by higher KOH (10.4 s-1), OFP (331.7 µg m-3), RIR weighted value (1.2), and F(O3)-OFPT (15.5 ppbv h-1). High proportions of isoprene and OVOCs (oxygenated VOCs) to the total KOH and the OFPT method were demonstrated whereas results of OFP and RIR-weighted presented extra great impacts of aromatics on O3 formation. The OFPT approach captured the process that has already happened and included final O3 response to the original VOC, thus reliable for replicating VOC impacts. The comparison results of the four methods showed similarities when utilizing KOH and OFPT methods, which reveals that the potential applicability of simple KOH for contingency VOC control and more complex OFPT method for detailed VOC- and source-oriented control during policy-making. To investigate propulsion of VOC-involved O3 photochemistry, atmospheric oxidation capacity (AOC) was quantified by two atmospheric oxidation indexes (AOI). Both AOIp_G (7.0 × 107 molec cm-3 s-1, potential AOC calculated by oxidation reaction rates) and AOIe_G (8.5 µmol m-3, estimated AOC given redox electron transfer for oxidation products) were stronger on O3 episode days, indicating that AOC promoted the radical cycling initiated from VOC oxidation and subsequent O3 production. Result-oriented AOIe_G reasonably characterized actual AOC inferred by good linear correlation between AOIe_G and O3 concentrations compared to process-oriented AOIp_G. Therefore, with continuous NOx abatement, AOIe_G should be considered to represent actual AOC, also O3-inducing ability.

An unexpected catalyst dominates formation and radiative forcing of regional haze.

Although regional haze adversely affects human health and possibly counteracts global warming from increasing levels of greenhouse gases, the formation and radiative forcing of regional haze on climate remain uncertain. By combining field measurements, laboratory experiments, and model simulations, we show a remarkable role of black carbon (BC) particles in driving the formation and trend of regional haze. Our analysis of long-term measurements in China indicates declined frequency of heavy haze events along with significantly reduced SO2, but negligibly alleviated haze severity. Also, no improving trend exists for moderate haze events. Our complementary laboratory experiments demonstrate that SO2 oxidation is efficiently catalyzed on BC particles in the presence of NO2 and NH3, even at low SO2 and intermediate relative humidity levels. Inclusion of the BC reaction accounts for about 90-100% and 30-50% of the sulfate production during moderate and heavy haze events, respectively. Calculations using a radiative transfer model and accounting for the sulfate formation on BC yield an invariant radiative forcing of nearly zero W m-2 on the top of the atmosphere throughout haze development, indicating small net climatic cooling/warming but large surface cooling, atmospheric heating, and air stagnation. This BC catalytic chemistry facilitates haze development and explains the observed trends of regional haze in China. Our results imply that reduction of SO2 alone is insufficient in mitigating haze occurrence and highlight the necessity of accurate representation of the BC chemical and radiative properties in predicting the formation and assessing the impacts of regional haze.

Progress in quantitative research on the relationship between atmospheric oxidation and air quality.

Atmospheric oxidizing capacity (AOC) is an essential driving force of troposphere chemistry and self-cleaning, but the definition of AOC and its quantitative representation remain uncertain. Driven by national demand for air pollution control in recent years, Chinese scholars have carried out studies on theories of atmospheric chemistry and have made considerable progress in AOC research. This paper will give a brief review of these developments. First, AOC indexes were established that represent apparent atmospheric oxidizing ability (AOIe) and potential atmospheric oxidizing ability (AOIp) based on aspects of macrothermodynamics and microdynamics, respectively. A closed study refined the quantitative contributions of heterogeneous chemistry to AOC in Beijing, and these AOC methods were further applied in Beijing-Tianjin-Hebei and key areas across the country. In addition, the detection of ground or vertical profiles for atmospheric OH·, HO2·, NO3· radicals and reservoir molecules can now be obtained with domestic instruments in diverse environments. Moreover, laboratory smoke chamber simulations revealed heterogeneous processes involving reactions of O3 and NO2, which are typical oxidants in the surface/interface atmosphere, and the evolutionary and budgetary implications of atmospheric oxidants reacting under multispecies, multiphase and multi-interface conditions were obtained. Finally, based on the GRAPES-CUACE adjoint model improved by Chinese scholars, simulations of key substances affecting atmospheric oxidation and secondary organic and inorganic aerosol formation have been optimized. Normalized numerical simulations of AOIe and AOIp were performed, and regional coordination of AOC was adjusted. An optimized plan for controlling O3 and PM2.5 was analyzed by scenario simulation.

Significant coal combustion contribution to water-soluble brown carbon during winter in Xingtai, China: Optical properties and sources.

To understand the characteristics of atmospheric brown carbon (BrC), daily PM2.5 samples in Xingtai, a small city in North China Plain (NCP), during the four seasons of 2018-2019, were collected and analyzed for optical properties and chemical compositions. The light absorption at 365 nm (absλ=365 nm) displayed a strong seasonal variation with the highest value in winter (29.0±14.3 M/m), which was 3.2∼5.4-fold of that in other seasons. A strong correlation of absλ=365 nm with benzo(b)fluoranthene (BbF) was only observed in winter, indicating that coal combustion was the major source for BrC in the season due to the enhanced domestic heating. The mass absorbing efficiency of BrC also exhibited a similar seasonal pattern, and was found to correlate linearly with the aerosol pH, suggesting a positive effect of aerosol acidity on the optical properties and formation of BrC in the city. Positive matrix factorization (PMF) analysis further showed that on a yearly basis the major source for BrC was biomass burning, which accounted for 34% of the total BrC, followed by secondary formation (26.7%), coal combustion (21.3%) and fugitive dust (18%). However, the contribution from coal combustion was remarkably enhanced in winter, accounting for ∼40% of the total. Our work revealed that more efforts of "shifting coal to clean energy" are necessary in rural areas and small cities in NCP in order to further mitigate PM2.5 pollution in China.

Vehicular Emissions Enhanced Ammonia Concentrations in Winter Mornings: Insights from Diurnal Nitrogen Isotopic Signatures.

A general feature in the diurnal cycle of atmospheric ammonia (NH3) concentrations is a morning spike that typically occurs around 07:00 to 10:00 (LST). Current hypotheses to explain this morning's NH3 increase remain elusive, and there is still no consensus whether traffic emissions are among the major sources of urban NH3. Here, we confirmed that the NH3 morning pulse in urban Beijing is a universal feature, with an annual occurrence frequency of 73.0% and a rapid growth rate (>20%) in winter. The stable nitrogen isotopic composition of NH3 (δ15N-NH3) in winter also exhibited a significant diurnal variation with an obvious morning peak at 07:00 to 10:00 (-18.6‰, mass-weighted mean), higher than other times of the day (-26.3‰). This diurnal pattern suggests that a large fraction of NH3 in the morning originated from nonagricultural sources, for example, power plants, vehicles, and coal combustion that tend to have higher δ15N-NH3 emission signatures relative to agricultural emissions. In particular, the contribution from vehicular emissions increased from 18% (00:00 to 07:00) to 40% (07:00 to 10:00), while the contribution of fertilizer sources to NH3 was reduced from 15.8% at 00:00 to 07:00 to 5.2% at 07:00 to 10:00. We concluded that NH3 concentrations in winter mornings in urban Beijing were indeed enhanced by vehicle emissions, which should be considered in air pollution regulations.

Observational Insights into Isoprene Secondary Organic Aerosol Formation through the Epoxide Pathway at Three Urban Sites from Northern to Southern China.

Isoprene is the most abundant precursor of global secondary organic aerosol (SOA). The epoxide pathway plays a critical role in isoprene SOA (iSOA) formation, in which isoprene epoxydiols (IEPOX) and/or hydroxymethyl-methyl-α-lactone (HMML) can react with nucleophilic sulfate and water producing isoprene-derived organosulfates (iOSs) and oxygen-containing tracers (iOTs), respectively. This process is complicated and highly influenced by anthropogenic emissions, especially in the polluted urban atmospheres. In this study, we took a 1-year measurement of the paired iOSs and iOTs formed through the IEPOX and HMML pathways at the three urban sites from northern to southern China. The annual average concentrations of iSOA products at the three sites ranged from 14.6 to 36.5 ng m-3. We found that the nucleophilic-addition reaction of isoprene epoxides with water dominated over that with sulfate in the polluted urban air. A simple set of reaction rate constant could not fully describe iOS and iOT formation everywhere. We also found that the IEPOX pathway was dominant over the HMML pathway over urban regions. Using the kinetic data of IEPOX to estimate the reaction parameters of HMML will cause significant underestimation in the importance of HMML pathway. All these findings provide insights into iSOA formation over polluted areas.

Molecular Composition of Oxygenated Organic Molecules and Their Contributions to Organic Aerosol in Beijing.

The understanding at a molecular level of ambient secondary organic aerosol (SOA) formation is hampered by poorly constrained formation mechanisms and insufficient analytical methods. Especially in developing countries, SOA related haze is a great concern due to its significant effects on climate and human health. We present simultaneous measurements of gas-phase volatile organic compounds (VOCs), oxygenated organic molecules (OOMs), and particle-phase SOA in Beijing. We show that condensation of the measured OOMs explains 26-39% of the organic aerosol mass growth, with the contribution of OOMs to SOA enhanced during severe haze episodes. Our novel results provide a quantitative molecular connection from anthropogenic emissions to condensable organic oxidation product vapors, their concentration in particle-phase SOA, and ultimately to haze formation.

Significant reduction in atmospheric organic and elemental carbon in PM2.5 in 2+26 cities in northern China.

To better understand the change characteristics and reduction in organic carbon (OC) and elemental carbon (EC) in particulate matter (PM) with a diameter of ≤2.5 µm (PM2.5) driven by the most stringent clean air policies and pandemic-related lockdown measures in China, a comprehensive field campaign was performed to measure the carbonaceous components in PM2.5 on an hourly basis via harmonized analytical methods in the Beijing-Tianjin-Hebei and its surrounding region (including 2 + 26 cities) from January 1 to December 31, 2020. The results indicated that the annual average concentrations of OC and EC reached as low as 6.6 ± 5.7 and 1.8 ± 1.9 µg/m3, respectively, lower than those obtained in previous studies, which could be attributed to the effectiveness of the Clean Air Action Plan and the impact of the COVID-19-related lockdown measures implemented in China. Marked seasonal and diurnal variations in OC and EC were observed in the 2 + 26 cities. Significant correlations (p < 0.001) between OC and EC were found. The annual average secondary OC levels level ranged from 1.8-5.4 µg/m3, accounting for 37.7-73.0% of the OC concentration in the 2 + 26 cities estimated with the minimum R squared method. Based on Interagency Monitoring of Protected Visual Environments (IMPROVE) algorithms, the light extinction contribution of carbonaceous PM to the total amount reached 21.1% and 26.0% on average, suggesting that carbonaceous PM played a less important role in visibility impairment than did the other chemical components in PM2.5. This study is expected to provide an important real-time dataset and in-depth analysis of the significant reduction in OC and EC in PM2.5 driven by both the Clean Air Action Plan and COVID-19-related lockdown policies over the past few years, which could represent an insightful comparative case study for other developing countries/regions facing similar carbonaceous PM pollution.

Drivers of improved PM2.5 air quality in China from 2013 to 2017.

From 2013 to 2017, with the implementation of the toughest-ever clean air policy in China, significant declines in fine particle (PM2.5) concentrations occurred nationwide. Here we estimate the drivers of the improved PM2.5 air quality and the associated health benefits in China from 2013 to 2017 based on a measure-specific integrated evaluation approach, which combines a bottom-up emission inventory, a chemical transport model, and epidemiological exposure-response functions. The estimated national population-weighted annual mean PM2.5 concentrations decreased from 61.8 (95%CI: 53.3-70.0) to 42.0 µg/m3 (95% CI: 35.7-48.6) in 5 y, with dominant contributions from anthropogenic emission abatements. Although interannual meteorological variations could significantly alter PM2.5 concentrations, the corresponding effects on the 5-y trends were relatively small. The measure-by-measure evaluation indicated that strengthening industrial emission standards (power plants and emission-intensive industrial sectors), upgrades on industrial boilers, phasing out outdated industrial capacities, and promoting clean fuels in the residential sector were major effective measures in reducing PM2.5 pollution and health burdens. These measures were estimated to contribute to 6.6- (95% CI: 5.9-7.1), 4.4- (95% CI: 3.8-4.9), 2.8- (95% CI: 2.5-3.0), and 2.2- (95% CI: 2.0-2.5) µg/m3 declines in the national PM2.5 concentration in 2017, respectively, and further reduced PM2.5-attributable excess deaths by 0.37 million (95% CI: 0.35-0.39), or 92% of the total avoided deaths. Our study confirms the effectiveness of China's recent clean air actions, and the measure-by-measure evaluation provides insights into future clean air policy making in China and in other developing and polluting countries.

The environmental benefit of Beijing-Tianjin-Hebei coal banning area for North China.

In order to achieve the targets specified in the Action Plan for Air Pollution Prevention and Control (APAPPC), a limited coal banning area (10,000 km2) was designated in the heavily polluted Beijing-Tianjin-Hebei region (BTH) for the first time in 2017. PM2.5 and elements were sampled by the network of BTH to evaluate the effectiveness of this policy. This study found that the fine days with PM2.5 < 75 µg m-3 accounted for 74.3% in the autumn and winter of 2017, which was significantly higher than that in 2016 (43%). The heavily polluted days (PM2.5 > 150 µg m-3) also decreased from 32.2% in 2016 to 4.9% in 2017. Arsenic (As) is an important tracer in coal consumption, which can be used to reflect the influence of the establishment of coal banning areas on north China. The cluster analysis of air mass forward trajectory identified that the number of polluted trajectories with PM2.5 and As in 2017 decreased by 47.6% and 49.7%, respectively. Under the implementation of the coal banning policy, the weighted concentration of PM2.5 and As decreased by 94.2 µg m-3 and 5.1 ng m-3 in the coal banning area, 60.9 µg m-3 and 3.4 ng m-3 in the no coal banning area in BTH, respectively. The influence of weighted concentration of PM2.5 and As in coal banning area on North China were 1.6-49.2 µg m-3 and 0.15-2.8 ng m-3, respectively, which was 38.8% and 29.7% lower than 2016. In coal banning area, BTH and other parts of North China, the reduction of the weight concentration of PM2.5 in 2017 accounted for 41.4%, 26.8% and 31.8% of the total reduction, respectively, so was the As in 39%, 26.3% and 34.6%, indicating that setting up a coal banning area scientifically in limited areas can produce remarkable regional benefit.

Significant contribution of secondary particulate matter to recurrent air pollution: Evidence from in situ observation in the most polluted city of Fen-Wei Plain of China.

Particulate matter (PM) pollution in high emission regions will affect air quality, human health and climate change on both local and regional scales, and thus attract worldwide attention. In this study, a comprehensive study on PM2.5 and its chemical composition were performed in Yuncheng (the most polluted city of Fen-Wei Plain of China) from November 28, 2020 to January 24, 2021. The average concentration of PM2.5 was 87.8 ± 52.0 µg/m3, which were apparently lower than those observed during the same periods of past five years, attributable to the clean air action plan implemented in this region. NO3- and organic carbon (OC) were the dominant particulate components, which on average contributed 22.6% and 16.5% to PM2.5, respectively. The fractions of NO3-, NH4+, OC and trace metals increased while those of crustal materials and elemental carbon decreased with the degradation of PM2.5 pollution. Six types of PM2.5 sources were identified by the PMF model, including secondary inorganic aerosol (35.3%), coal combustion (28.7%), vehicular emission (20.7%), electroplating industry (8.6%), smelt industry (3.9%) and dust (2.8%). Locations of each identified source were pinpointed based on conditional probability function, potential source contribution function and concentration weighted trajectory, which showed that the geographical distribution of the sources of PM2.5 roughly agreed with the areas of high emission. Overall, this study provides valuable information on atmospheric pollution and deems beneficial for policymakers to take informed action to sustainably improve air quality in highly polluted region.

Characterization and source identification of submicron aerosol during serious haze pollution periods in Beijing.

Submicron aerosol is of extensive concern not only due to its significant impact on air quality but also because it is detrimental to human health. In this study, we investigated the characteristics, sources and chemical processes of submicron aerosol based on real-time online measurements of submicron aerosols (NR-PM1) during December 2015 at an urban site in Beijing. The average mass concentration of NR-PM1 was 92.5±84.9 µg/m3, the hourly maximum was 459.1 µg/m3 during the entire observation. The organic aerosol (OA) (55%) was the largest contributor to NR-PM1. The average mass concentration of PAHs was 0.217±0.247 µg/m3, exhibiting the highest concentration at night and the lowest levels in the daytime. The average mass concentration of organic nitrate was 2.52±2.36 µg/m3 and that of inorganic nitrate was 7.62±8.22 µg/m3, accounting for 36% and 64%, respectively, of the total nitrate mass. Positive matrix factorization (PMF) differentiated the OA into five chemical components including LV-OOA, SV-OOA, COA, HOA and CCOA, accounting for 22%, 16%, 13%, 25% and 24% respectively, of the total OA. The average NR-PM1 mass concentration on the heavy polluted days (HPD) was 182.8±70.2 µg/m3, which was approximately 9 times that on clean days (CD). The enhanced secondary formation of SNA was evident on HPD, especially the rapid increase of sulfate (23%) and nitrate (19%).

Annual nonmethane hydrocarbon trends in Beijing from 2000 to 2019.

High loads of ground-level ozone have occurred with the implementation of the Air Pollution Prevention and Control Action Plan. However, the long temporal variation in precursor nonmethane hydrocarbons (NMHCs) has rarely been studied. In this study, we examined the evolution of NMHCs in Beijing based on ambient measurements from 2000 to 2019. The results indicated that the annual variation of ambient NMHCs during 2000 and 2019 could be divided into two stages. The mixing ratios of NMHCs rapidly rose during 2000 and 2009 (1.76 ppbv/year) but exhibited a downward trend from 2009 to 2019 at rate of 0.80 ppbv/yr. Moreover, the notable decrease in alkenes and aromatics after 2009 led to a sharp decrease in the propylene-equivalent concentration (PEC) (-0.80 ppbv/year). Implementation of emission reduction measures in Beijing have effectively reduced the contribution of vehicle-related sources, but the contribution of solvent usage and fuel consumption increased, which will become the focus of VOC control in Beijing in the future.

Source apportionment of PM2.5 and visibility in Jinan, China.

Atmospheric extinction is impacted by the chemical composition of particles. To better understand the chemical composition of PM2.5 (particles with diameters of less than 2.5 µm) and its relationship with extinction, one-month sampling campaigns were carried out in four different seasons from 2013 to 2014 in Jinan, China. The seasonal average concentrations of PM2.5 were 120.9 (autumn), 156.6 (winter), 102.5 (spring), and 111.8 µg/m3 (summer). The reconstructed PM2.5 chemical composition showed that sulfate, nitrate, chlorine salt, organic matter (OM), mineral dust, elemental carbon (EC) and others accounted for 25%, 14%, 2%, 24%, 22%, 3% and 10%, respectively. The relationship between the chemical composition of PM2.5 and visibility was reconstructed by the IMPROVE method, and ammonium sulfate, ammonium nitrate, OM and EC dominated the visibility. Seven main sources were resolved for PM2.5, including secondary particles, coal combustion, biomass burning, industry, motor vehicle exhaust, soil dust and cooking, which accounted for 37%, 21%, 13%, 13%, 12%, 3% and 1%, respectively. The contributions of different sources to visibility were similar to those to PM2.5. With increasing severity of air pollution, the contributions of secondary particles and coal combustion increased, while the contribution of motor vehicle exhaust decreased. The results showed that coal combustion and biomass burning were still the main sources of air pollution in Jinan.

Significant contribution of spring northwest transport to volatile organic compounds in Beijing.

High values of ozone (O3) occur frequently in the dry spring season; thus, understanding the evolution characteristics of volatile organic compounds (VOCs) in spring is of great significance for preventing O3 pollution. In this study, a total of 101 VOCs from April 16 to May 21, 2019, were quantified using an online gas chromatography mass spectrometer/flame ionization detector (GCMS/FID). The results indicated that the observed concentration of total VOCs (TVOCs) was 30.4 ± 17.0 ppbv, and it was dominated by alkanes (44.3%), followed by oxygenated VOCs (OVOCs) (17.4%), halocarbons (12.7%), aromatics (9.5%), alkenes (8.2%), acetylene (5.3%) and carbon disulfide (2.5%). The average mixing ratio of VOCs showed obvious diurnal variation (high at night, low during daytime). We conducted a source apportionment study based on 32 major VOCs using positive matrix factorization (PMF), and coal + biomass burning (25.2%), diesel exhaust (16.0%), gasoline exhaust + evaporation (17.4%), secondary + long-lived species (16.7%), biogenic sources (4.3%), industrial emissions (9.3%) and solvent use (11.2%) were identified as major sources of VOCs. In addition to local emissions, most of the atmospheric VOCs were derived from long-distance air masses (65.7%), and the average mixing ratio of VOCs in the northwest direction was 29.4 ppbv. Combined with the results of the potential source contribution function (PSCF) indicate that research should focus on the local emissions of combustion, transportation sources and solvents usage to control atmospheric VOCs. Additionally, transmission of the northwest air mass is an important component that cannot be ignored during spring in Beijing.

Chemical characteristics and source apportionment of PM2.5 in a petrochemical city: Implications for primary and secondary carbonaceous component.

To study the pollution features and underlying mechanism of PM2.5 in Luoyang, a typical developing urban site in the central plain of China, 303 PM2.5 samples were collected from April 16 to December 29, 2015 to analyze the elements, water soluble inorganic ions, organic carbon and elemental carbon. The annual mean concentration of PM2.5 was 142.3 µg/m3, and 75% of the daily PM2.5 concentrations exceeded the 75 µg/m3. The secondary inorganic ions, organic matter and mineral dust were the most abundant species, accounting for 39.6%, 19.2% and 9.3% of the total mass concentration, respectively. But the major chemical components showed clear seasonal dependence. SO42- was most abundant specie in spring and summer, which related to intensive photochemical reaction under high O3 concentration. In contrast, the secondary organic carbon and ammonium while primary organic carbon and ammonium significantly contributed to haze formation in autumn and winter, respectively. This indicated that the collaboration effect of secondary inorganic aerosols and carbonaceous matters result in heavy haze in autumn and winter. Six main sources were identified by positive matrix factorization model: industrial emission, combustion sources, traffic emission, mineral dust, oil combustion and secondary sulfate, with the annual contribution of 24%, 20%, 24%, 4%, 5% and 23%, respectively. The potential source contribution function analysis pointed that the contribution of the local and short-range regional transportation had significant impact. This result highlighted that local primary carbonaceous and precursor of secondary carbonaceous mitigation would be key to reduce PM2.5 and O3 during heavy haze episodes in winter and autumn.

Characteristics of PM2.5 pollution in Beijing after the improvement of air quality.

Following the implementation of the strictest clean air policies to date in Beijing, the physicochemical characteristics and sources of PM2.5 have changed over the past few years. To improve pollution reduction policies and subsequent air quality further, it is necessary to explore the changes in PM2.5 over time. In this study, over one year (2017-2018) field study based on filter sampling (TH-150C; Wuhan Tianhong, China) was conducted in Fengtai District, Beijing, revealed that the annual average PM2.5 concentration (64.8 ± 43.1 µg/m3) was significantly lower than in previous years and the highest PM2.5 concentration occurred in spring (84.4 ± 59.9 µg/m3). Secondary nitrate was the largest source and accounted for 25.7% of the measured PM2.5. Vehicular emission, the second largest source (17.6%), deserves more attention when considering the increase in the number of motor vehicles and its contribution to gaseous pollutants. In addition, the contribution from coal combustion to PM2.5 decreased significantly. During weekends, the contribution from EC and NO3- increased whereas the contributions from SO42-, OM, and trace elements decreased, compared with weekdays. During the period of residential heating, PM2.5 mass decreased by 23.1%, compared with non-heating period, while the contributions from coal combustion and vehicular emission, and related species increased. With the aggravation of pollution, the contribution of vehicular emission and secondary sulfate increased and then decreased, while the contribution of NO3- and secondary nitrate continued to increase, and accounted for 34.0% and 57.5% of the PM2.5 during the heavily polluted days, respectively.

Different HONO Sources for Three Layers at the Urban Area of Beijing.

Gaseous nitrous acid (HONO) is a crucial precursor of the hydroxyl (OH) radical, which is a "detergent" in the atmosphere. Nowadays, HONO formation mechanisms at polluted urban areas are controversial, which restricts the understanding of atmospheric oxidative capacity and radical cycling. Herein, multiday vertical observation of HONO and NOx was simultaneously performed at three heights at the urban area of Beijing for the first time. The vertical distribution of HONO was often unexpected, and it had the highest HONO concentration at 120 m, followed by those at 8 and 240 m. 0D box model simulations suggest that ground and aerosol surfaces might play similar roles in NO2 conversion at 8 m during the whole measurement. NO2 conversion on aerosol surfaces was the most important HONO source aloft during haze days. At daytime, a strong missing HONO source unexpectedly existed in the urban aloft, and it was relevant to solar radiation and consumed OH.

Seasonal variation and sources of derivatized phenols in atmospheric fine particulate matter in North China Plain.

Qualitative and quantitative analyses of derivatized phenols in Beijing and in Xinglong were performed from 2016 to 2017 using gas chromatography-mass spectrometry. The results showed substantially more severe pollution in Beijing. Of the 14 compounds detected, the total average concentration was 100 ng/m3 in Beijing, compared with 11.6 ng/m3 in Xinglong. More specifically, concentration of nitro-aromatic compounds (NACs) (81.9 ng/m3 in Beijing and 8.49 ng/m3 in Xinglong) was the highest, followed by aromatic acids (14.6 ng/m3 in Beijing and 2.42 ng/m3 in Xinglong) and aromatic aldehydes (3.62 ng/m3 in Beijing and 0.681 ng/m3 in Xinglong). In terms of seasonal variation, the highest concentrations were found for 4-nitrocatechol in winter in Beijing (79.1 ± 63.9 ng/m3) and 4-nitrophenol in winter in Xinglong (9.72 ± 8.94 ng/m3). The analysis also revealed diurnal variations across different seasons. Most compounds presented higher concentrations at night in winter because of the decreased boundary layer height and increased heating intensity. While some presented higher levels during the day, which attributed to the photo-oxidation process for summer and more biomass burning activities for autumn. Higher concentrations appeared in winter and autumn than in spring and summer, which resulted from more coal combustions and adverse meteorological conditions. The significant correlations among NACs indicated similar sources of pollution. Higher correlations presented within each subgroup than those between the subgroups. Good correlations between levoglucosan and nitrophenols, nitrocatechols, nitrosalicylic acids, with correlation coefficients (r) of 0.66, 0.69 and 0.69, respectively, indicating an important role of biomass burning among primary sources.

Meteorological mechanism for a large-scale persistent severe ozone pollution event over eastern China in 2017.

An intensive and persistent regional ozone pollution event occurred over eastern China from 25 June to 5 July 2017. 73 out of 96 selected cities, most located in the Beijing-Tianjin-Hebei and the surrounding area (BTHS), suffered severe ozone pollution. A north-south contrast ozone distribution, with higher ozone (199 ± 33 µg/m3) in the BTHS and lower ozone (118 ± 25 µg/m3) in the Yangtze River Delta (YRD), was found to be dominated by the position of the West Pacific Subtropical High (WPSH) and mid-high latitude wave activities. In the BTHS, the positive anomalies of geopotential height at 500 hPa and temperature at the surface indicated favorable meteorological conditions for local ozone formation. Prevailing northwesterly winds in the mid-high troposphere and warm advection induced by weak southerly winds in the low troposphere resulted in low-moderate relative humidity (RH), less total cloud cover (TCC), strong solar radiation and high temperatures. Moreover, southerly winds prevailing over the BTHS aggravated the pollution due to regional transportation of O3 and its precursors. On one hand, the deep sinking motion and inversion layer suppressed the dispersion of pollutants. On the other hand, O3-rich air in the upper layer was maintained at night due to temperature inversion, which facilitated O3 vertical transport to the surface in the next-day morning due to elevated convection. Generally, temperature, UV radiation, and RH showed good correlations with O3 in the BTHS, with rates of 8.51 (µg/m3)/°C (within the temperature range of 20-38°C), 59.54 (µg/m3)/(MJ/m2) and -1.93 (µg/m3)/%, respectively.