Insights into the phenomenon of an explosive growth and sharp decline in haze: A case study in Beijing.

A severe haze episode occurred in winter in the North China Plain (NCP), and the phenomenon of an explosive growth and sharp decline in PM2.5 (particulate matter with an aerodynamic diameter equal to or less than 2.5 µm) concentration was observed. To study the systematic causes for this phenomenon, comprehensive observations were conducted in Beijing from November 26 to December 2, 2015; during this period, meteorological parameters, LIDAR data, and the chemical compositions of aerosols were determined. The haze episode was characterized by rapidly varying PM2.5 concentration, and the highest PM2.5 concentration reached 667 µg/m3. During the haze episode, the NCP was dominated by a weak high-pressure system and continuously low PBL (planetary boundary layer) heights, which are unfavorable conditions for the diffusion of pollutants. The large increases in the concentrations of SNA (SO42-, NO3- and NH4+) during the haze implied that the formation of SNA was the largest contribution. Water vapor also played a vital role in the formation of haze by promoting the chemical transformation of secondary pollutants, which led to higher PM2.5 concentrations. The spatial distributions of PM2.5 in Beijing at different times and the backward trajectories of the air masses also indicated that pollutants from surrounding provinces in particular, contributed to the higher PM2.5 concentration.

Abundant oxygenated volatile organic compounds and their contribution to photochemical pollution in subtropical Hong Kong.

Volatile organic compounds (VOCs), which are ubiquitous pollutants in the urban and regional atmosphere, promote the formation of ozone (O3) and secondary organic aerosols, thereby significantly affecting the air quality and human health. The ambient VOCs at a coastal suburban site in Hong Kong were continuously measured using proton-transfer-reaction time-of-flight mass spectrometry (PTR-ToF-MS) from November 2020 to December 2020. 83 VOC species, including 23 CxHy, 53 CxHyO1-3, and 7 nitrogen-containing species, were measured during the campaign, with a mean concentration of 36.75 ppb. Oxygenated VOCs (OVOCs) accounted for most (77.4%) of the measured species, including CxHyO1 (50.7%) and CxHyO2 (25.1%). The measured VOC species exhibited distinct temporal and diurnal variations. High concentrations of isoprene and OVOCs were measured in autumn with more active photochemistry, whereas large evening peaks of aromatics from local and regional primary emissions were prominent in winter. The OH reactivity and O3 formation potential (OFP) of key precursors were quantified. OVOCs contributed about half of the total OH reactivity and OFP, followed by alkenes and aromatics, and the contribution of aromatics increased significantly in winter. The potential source contribution function was used to investigate the potential source regions associated with high VOC concentrations. Through positive matrix factorization analysis, six major sources were identified based on fingerprint molecules. The contributions of biogenic sources and secondary formation to the observed species were notable in late autumn, whereas vehicle emissions and solid fuel combustion had higher contributions in winter. The findings highlight the important role of OVOCs in photochemical pollution and provide valuable insights for the development of effective pollution control strategies.

Development of an enhanced method for atmospheric carbonyls and characterizing their roles in photochemistry in subtropical Hong Kong.

Carbonyl compounds are ubiquitous and play vital roles in tropospheric photochemistry and oxidation capacity, particularly affecting radical cycling and ozone formation. An enhanced method based on ultra-high-performance liquid chromatography and electrospray ionization tandem mass spectrometry was developed to simultaneously quantify 47 carbonyl compounds with carbon (C) numbers from 1 to 13. Applying this new method to samples collected at ground and ship-borne field campaigns, we investigated the abundance, characteristic distribution, and photochemical activity of carbonyl species in the coastal atmosphere of Hong Kong. The total concentration of detected carbonyls ranged from 9.1 to 32.7 ppbv and exhibited distinct spatial variability. In addition to the usual abundant carbonyl species (formaldehyde, acetaldehyde, and acetone), aliphatic saturated aldehydes with C ≥ 5 (particularly hexaldehyde and nonanaldehyde), and di­carbonyls, exhibit significant abundance and photochemical reactivity in the coastal site and on the sea. The measured carbonyls could contribute to an estimated peroxyl radical formation rate of 1.88-8.43 ppb/h via OH oxidation and photolysis, greatly enhancing oxidation capacity and radical cycling. The ozone formation potential (OFP) estimated from the maximum incremental reactivity (MIR) was dominated (69 %-82 %) by formaldehyde and acetaldehyde, with significant contribution (4 %-13 %) from di­carbonyls. Furthermore, another dozens of long-chain carbonyls without MIR values, which were typically below detection or not included in the conventional analytical method, would increase the ozone formation rate by an additional 2 %-33 %. Additionally, the glyoxal, methylglyoxal, benzaldehyde and other α, ß-unsaturated aldehydes also exhibited considerable contribution to secondary organic aerosol (SOA) formation potential. This study highlights the importance of various reactive carbonyls in the atmospheric chemistry of urban and coastal regions. The newly developed method can effectively characterize more carbonyl compounds and advance our understanding of their roles in photochemical air pollution.

Impact of clean air action on the PM2.5 pollution in Beijing, China: Insights gained from two heating seasons measurements.

Comprehensive observations have been carried out in Beijing to investigate the impact of the Clean Air Action implemented in 2013 on changes in aerosol chemistry characteristics in heating seasons of 2016-2017 and 2017-2018. Results showed that PM2.5, SO2, NO2, NH3, O3 and CO concentrations decreased by 40.9%, 46.0%, 29.0%, 40.6%, 11.0% and 44.4%, respectively. Significant decreases were also observed for NO3- (32.5%), SO42- (52.9%), NH4+ (56.0%), Cl- (64.6%) and K+ (68.2%), on average. Enhanced PM2.5 pollution has changed from sulfate-driven to nitrate-driven. The decrease in SO2 was more significant than NO2 as a response to one reason of the larger decrease in SO42- concentration. The formation of sulfate was dominated by heterogeneous reactions in two heating seasons. Low pH could facilitate more efficient conversion of SO2 to sulfate. Photochemical reactions played a much more important role in the formation of nitrate in the second heating season, especially in the daytime. The major source regions for sulfate and nitrate were identified by back trajectories and the potential source function (PSCF). More nitrate was brought into Beijing when air masses coming from polluted regions in the southwest prevailed in 2017-2018 heating season. Thus, regional joint prevention and control are of great importance in the achievement of an effective reduction in PM2.5 pollution in the future.

Characteristics and sources of volatile organic compounds during high ozone episodes: A case study at a site in the eastern Guanzhong Plain, China.

This study performed continuous measurements of 105 volatile organic compounds (VOCs) in Weinan in the eastern Guanzhong Plain from 1 July to September 19, 2019. Ozone (O3) episode and non-episode days were identified according to China Ambient Air Quality Standard, and the concentrations of total quantified VOCs (TVOCs) were 33.43 ± 13.64 ppbv and 29.13 ± 14.31 ppbv, respectively. During different O3 pollution episodes, alkanes comprised the highest proportion to TVOC concentrations, while alkenes contributed the most to ozone formation potential (OFP). In addition, O3 episode days were mainly caused by enhanced emissions of precursors and meteorological conditions favorable to O3 production. Based on Empirical Kinetic Modelling Approach (EKMA), the O3 formation in Weinan was found in the transitional regime, in which the synergistic reduction of VOCs and nitrogen oxide (NOx) would be more effective for O3 reduction. Eight sources were identified by positive matrix factorization (PMF) model, with natural gas (NG)/liquefied petroleum gas (LPG) usage as the most significant contributor to VOC concentration, followed by vehicle exhaust, biomass burning, solvent usage, fuel evaporation, rubber/plastic industrial emissions, biogenic source, and mixed industrial emissions. Furthermore, rubber/plastic industrial emissions, solvent usage, fuel evaporation, and vehicle exhaust were the most significant sources to O3 formation. Based on conditional bivariate probability function (CBPF), vehicle exhaust, fuel evaporation, and solvent usage were mainly local emissions, while other sources were mainly affected by regional transport. This study provides useful reference for research on the atmospheric photochemical formation of O3 and evidence for regional O3 reduction strategies.

Characterization and sources of volatile organic compounds (VOCs) and their related changes during ozone pollution days in 2016 in Beijing, China.

Concentrations of 99 volatile organic compounds (VOCs) were continuously measured online at an urban site in Beijing, China, in January, April, July, and October 2016. Characterization and sources of VOCs and their related changes during days with heavy ozone (O3) pollution were analysed. The total observed concentration of VOCs (TVOCs) was 44.0 ± 28.9 ppbv. The VOC pollution level has decreased in Beijing but remains higher than in other Chinese cities. Alkanes comprised the highest proportion among seven major sampled VOC groups. The concentrations and sources of ambient VOCs showed obvious temporal variations. Six emission sources were identified by the positive matrix factorization (PMF), including biomass burning, coal combustion, gasoline vehicles, diesel vehicles, solvent usage, and biogenic + secondary emissions. The combustion source was the key control factor for VOC reduction in Beijing. From the potential source contribution function (PSCF) and concentration-weighted trajectory (CWT) model, Beijing, Tianjin, Hebei, Shanxi, Inner Mongolia, Shandong, and Henan were identified as major potential source regions of ambient VOCs. O3 formation was sensitive to VOCs in Beijing according to the VOC/NOx ratio (ppbC/ppbv, 8:1 threshold). High- and low-O3 days in July were identified, and high O3 levels were due to both enhanced VOC emission levels and meteorological conditions favourable to the production of O3. These findings provide evidence that the fuel combustion and regional transport have a great impact on concentrations and sources of VOCs in urban Beijing.

VOC characteristics, sources and contributions to SOA formation during haze events in Wuhan, Central China.

Based on detailed data on 102 volatile organic compounds (VOCs) measured continuously from 2016.10.9 to 2016.11.17 in Wuhan, the VOC characteristics, secondary organic aerosol (SOA) characteristics, SOA formation potential (SOAP), potential source regions, sources and contributions during different haze episodes were analyzed. The total VOC (TVOC) concentrations on clear days (visibility >10 km), slight haze days (visibility of 5-10 km), and severe haze days (visibility <5 km) were 34.87 ±â€¯14.89 ppbv, 45.06 ±â€¯26.69 ppbv, and 49.55 ±â€¯24.82 ppbv, respectively. The SOAP on haze days (447.04 ±â€¯253.85 ppbv) was significantly higher than that on clear days (300.62 ±â€¯138.48 ppbv), and aromatics were the dominant contributors to SOA formation under different visibility conditions, accounting for approximately 97% of the total SOAP. The ratio of ethylbenzene to m/p-xylene (E/X) indicated that atmospheric photochemical reactions were slightly stronger on haze days. The ratio of toluene to benzene (T/B) indicated that vehicle exhaust had significant effects on VOCs, but no significant changes occurred during different haze episodes. The ratio of benzene, toluene, ethylbenzene and xylenes (BTEX) to CO indicated that VOCs from solvent usage in painting/coating and industrial emissions increased with increasing haze pollution. Based on backward trajectories and the potential source contribution function (PSCF), short-distance transport was the main source influencing VOC pollution, especially transport from the southwest. Seven sources were identified by positive matrix factorization (PMF): industrial sources, vehicular exhaust, solvent usage in painting/coating, fuel evaporation, liquefied petroleum gas (LPG) usage, biogenic sources and biomass burning. Moreover, solvent usage in painting/coating, vehicle exhaust and LPG usage were the most important sources that significantly aggravated VOC pollution during haze events. The results can provide references for local governments developing control strategies of VOCs during haze pollution events.