Ozone Pollution Episodes Research Articles

Unravelling the impacts of stratospheric intrusions on near-surface ozone during the springtime ozone pollution episodes in Lhasa, China

While air pollution due to fine particulate matter (PM2.5) has been effectively controlled in China; the photochemical pollution characterized by elevated ozone (O3) has emerged as a major concern for air quality improvement. Except for ozone, Lhasa is one of the cleanest cities in China with the lowest annual PM2.5 concentration in 2017. The levels of major air pollutants in Lhasa are much lower than those of other cities in the eastern region of China, especially in May, when the O3 concentration peaks. This study was based on multi-source observations in combination with the Goddard Earth Observing System coupled with chemistry (GEOS-Chem) and the Hybrid Single Particle Lagrangian Integrated Trajectory (HYSPLIT) models to explore the causes of O3 pollution in Lhasa in May 2023. The results indicated that during the high O3 episodes, the concentrations of O3 precursors were low in Lhasa. Surrounding cities in other parts of the Tibetan Plateau also experienced high ozone concentrations despite being in different airsheds, suggesting that the O3 pollution in Lhasa was caused by regional transport rather than purely local emissions. Stratospheric intrusion events modulated by the westerly jet led to elevated ozone in the troposphere above Lhasa City. The results of the GEOS-Chem model indicated that horizontal advection, turbulence, diffusion, and other effects led to high concentrations of ozone in the near-surface above Lhasa. Vertical transport was the dominant factor leading to ozone concentration increases during high ozone days, with a contribution of 6.33 Gg/day. In addition, high-altitude air masses with a maximum altitude of over 8000 m, were observed arriving in Lhasa during the high ozone days. This study revealed that stratospheric intrusions have a greater contribution to the high O3 concentration in Lhasa in spring and provided a scientific basis for mitigating O3 pollution in the plateau cities.

Ground-based MAX-DOAS observations of tropospheric formaldehyde and nitrogen dioxide: Insights into ozone formation sensitivity

Tropospheric profiles of HCHO, NO2, and O3 are important for analyzing ozone formation mechanism. In this study, ground-based multi-axis differential optical absorption spectroscopy (MAX-DOAS), light detection and ranging (LIDAR), and in-situ measurements were simultaneously performed to diagnose ozone formation sensitivity at the Heshan Observatory in the Pearl River Delta (PRD) region from September to end October 2019. The profiles of tropospheric HCHO and NO2 were retrieved from MAX-DOAS measurements using an optimal estimation method. The retrieved surface HCHO and NO2 results were validated with 2,4-dinitrophenylhydrazine (DNPH) and Thermo 42i measurements, and the correlation coefficients (R) were 0.78 and 0.81, respectively. The retrieved tropospheric vertical column densities (VCDs) of HCHO and NO2 were compared with TROPOMI measurements, and the correlation coefficients (R) were 0.68 and 0.87, respectively. In addition, MAX-DOAS and LIDAR measurements were combined to diagnose a typical planetary boundary layer (PBL) ozone pollution episode from September 28 to October 10, 2019; this episode was analyzed using HCHO/NO2 ratio as an indicator and was found to be dominated by the VOC-sensitive regime. Moreover, the regime transition of ozone formation sensitivity was calculated using the surface HCHO/NO2 ratio and increased O3 from the MAX-DOAS and Thermo 49i measurements, with transition thresholds of 1.43 and 1.78, respectively. Based on this definition, the ozone formation sensitivity at Heshan Observatory varied from VOC-sensitive (< 0.2 km and > 0.8 km) to NOx-sensitive (0.3–0.7 km) to VOC-NOx-sensitive (0.2–0.3 km and 0.7–0.8 km). The results improve our understanding of ozone formation sensitivity in the PRD region.

Ozone production sensitivity analysis for the Chengdu Plain Urban Agglomeration based on a multi-site and two-episode observation

Chengdu Plain Urban Agglomeration (CPUA) is one of the most serious areas suffering from ozone pollution in China. A comprehensive field observation focused on the ozone production rate and its sensitivity was conducted at CPUA in the summer of 2019. Six sampling sites were set and two ozone pollution episodes were recognized. The daily maximum 8-h average (MDA8) O3 concentration reached 137.9 ppbv in the urban sites during the ozone pollution episode. Peak concentration of O3 was closely related to intense solar radiation, high temperatures, and precursor emissions. The OH-HO2-RO2 radical chemistry and ozone production rate (P(O3)) were calculated using an observation-based model (OBM). The daily peak OH concentration varied in the range of 3-13 × 106 molecules cm−3, and peak HO2 and RO2 were in the range of 2–14 × 108 molecules cm−3 during ozone pollution episodes. During the ozone pollution episode, the average maximum of P(O3) in suburban sites (about 30 ppbv h-1.) was compared with urban sites, and the maximum of P(O3) was 18 ppbv h-1 in rural sites. The relative incremental reactivity (RIR) results demonstrate that it was a VOCs-limited regime in the central urban area of Chengdu, with NOx suppression effect in some regions. In the southern neighboring suburb of Chengdu, it was VOCs-limited as well. However, the northern suburban area was a transition region. In the remote rural areas of the southern CPUA, it was highly NOx-limited. Local ozone production driven by the photochemical process is crucial to the ozone pollution formation in CPUA. The geographically differentiated recognition of the ozone regime found by this study can help to tailor control strategies for local conditions and avoid the negative effects of a one-size-fits-all approach.

Comprehensive measurement of carbonyls in Lhasa, Tibetan Plateau: Implications for strong atmospheric oxidation capacity

Carbonyls are ubiquitous in the troposphere and play a crucial role in atmospheric oxidation capacity (AOC), particularly in photochemistry-active regions such as the Tibetan Plateau (TP). However, the composition and evolution of carbonyls over the TP is still poorly understood due to a lack of comprehensive observations and modelling. Here, we conducted an intensive field measurement of 37 carbonyls and their precursors at a suburban site in Lhasa during summer 2022. Markedly higher levels of carbonyls (7.24 ± 3.83 ppbv) were found during ozone pollution episodes, with 36 % higher than those during non-episodes. Formaldehyde was the most abundant carbonyl (38 %), which primarily originating from photochemical secondary formations. Simulations using the Rapid adaptive Optimization Model for Atmospheric Chemistry (ROMAC) indicated strong AOC in Lhasa, with the daytime maximum of ·OH and ·HO2 of 9.8 × 106 and 4.2 × 108 molecules cm−3, respectively, which were even higher than that in most of the megacities in China. Notably, AOC significantly enhanced with the increasing carbonyls during the episodes, with the concentrations of ·OH and ·HO2 were boosted 21 % and 67 % than those during non-episodes, respectively. Budget analysis revealed that the ·HO2 + NO (88 %) and ·OH + VOC (74 %) pathways dominated the generation and loss of ·OH, respectively. And for ·HO2, they were ·RO2 + NO (67 %) and ·HO2 + NO (83 %). This study provides valuable insights into the strong AOC in the ecologically-fragile and climate-sensitive TP region, and highlighted the crucial role of anthropogenic–biogenic interactions in the active photochemistry of TP.

Projecting Changes in the Frequency and Magnitude of Ozone Pollution Events Under Uncertain Climate Sensitivity

AbstractClimate change is projected to worsen ozone pollution over many populated regions, with larger impacts at higher concentrations. More intense and frequent ozone episodes risk setbacks to human health and environmental policy achievements. However, assessing these changes is complicated by uncertain climate sensitivity, closely related to climate model response, and internal variability in simulations projecting climate's influence on air quality. Here, leveraging a global modeling framework that one‐way couples a human activity model, an Earth system model of intermediate complexity, and an atmospheric chemistry model, we investigate the role of climate sensitivity in climate‐induced changes to high ozone pollution episodes in the United States using multiple greenhouse gas emissions scenarios, representations of climate sensitivity, and initial condition members. We bias correct and evaluate historical model simulations, identifying modeled and observed O3 episodes using extreme value theory, and extend the approach to projections of mid‐ and end‐century climate impacts. Results show that the influence of climate sensitivity can be as significant as that of greenhouse gas emissions scenario absent precursor emissions changes. Climate change is projected to increase the magnitude of the highest annually occurring O3 concentrations by over 2.3 ppb on average across the U.S. at mid‐century under a high climate sensitivity and moderate emissions scenario, but the increase is limited to less than 0.3 ppb under lower climate sensitivity. Further, we show that areas in the U.S. currently meeting air quality standards risk being pushed into non‐compliance due to a climate‐induced increase in frequency of high ozone days.

Quantifying the contributions of meteorology, emissions, and transport to ground-level ozone in the Pearl River Delta, China

Ozone pollution presents a growing air quality threat in urban agglomerations in China. It remains challenge to distinguish the roles of emissions of precursors, chemical production and transportations in shaping the ground-level ozone trends, largely due to complicated interactions among these 3 major processes. This study elucidates the formation factors of ozone pollution and categorizes them into local emissions (anthropogenic and biogenic emissions), transport (precursor transport and direct transport from various regions), and meteorology. Particularly, we attribute meteorology, which affects biogenic emissions and chemical formation as well as transportation, to a perturbation term with fluctuating ranges. The Community Multiscale Air Quality (CMAQ) model was utilized to implement this framework, using the Pearl River Delta region as a case study, to simulate a severe ozone pollution episode in autumn 2019 that affected the entire country. Our findings demonstrate that the average impact of meteorological conditions changed consistently with the variation of ozone pollution levels, indicating that meteorological conditions can exert significant control over the degree of ozone pollution. As the maximum daily 8-hour average (MDA8) ozone concentrations increased from 20 % below to 30 % above the National Ambient Air Quality Standard II, contributions from emissions and precursor transport were enhanced. Concurrently, direct transport within Guangdong province rose from 13.8 % to 22.7 %, underscoring the importance of regional joint prevention and control measures under adverse weather conditions. Regarding biogenic emissions and precursor transport that cannot be directly controlled, we found that their contributions were generally greater in urban areas with high nitrogen oxides (NOx) levels, primarily due to the stronger atmospheric oxidation capacity facilitating ozone formation. Our results indicate that not only local anthropogenic emissions can be controlled in urban areas, but also the impacts of local biogenic emissions and precursor transport can be potentially regulated through reducing atmospheric oxidation capacity.

Significance of Volatile Organic Compounds to Secondary Pollution Formation and Health Risks Observed during a Summer Campaign in an Industrial Urban Area.

The chemical complexity and toxicity of volatile organic compounds (VOCs) are primarily encountered through intensive anthropogenic emissions in suburban areas. Here, pollution characteristics, impacts on secondary pollution formation, and health risks were investigated through continuous in-field measurements from 1-30 June 2020 in suburban Nanjing, adjacent to national petrochemical industrial parks in China. On average, the total VOCs concentration was 34.47 ± 16.08 ppb, which was comprised mostly by alkanes (41.8%) and halogenated hydrocarbons (29.4%). In contrast, aromatics (17.4%) dominated the ozone formation potential (OFP) and secondary organic aerosol formation potential (SOAFP) with 59.6% and 58.3%, respectively. Approximately 63.5% of VOCs were emitted from the petrochemical industry and from solvent usage based on source apportionment results, followed by biogenic emissions of 22.3% and vehicle emissions of 14.2%. Of the observed 46 VOC species, hexachlorobutadiene, dibromoethane, butadiene, tetrachloroethane, and vinyl chloride contributed as high as 98.8% of total carcinogenic risk, a large fraction of which was ascribed to the high-level emissions during ozone pollution episodes and nighttime. Therefore, the mitigation of VOC emissions from petrochemical industries would be an effective way to reduce secondary pollution and potential health risks in conurbation areas.

Unveiling vertical ozone variation with UAV-Based monitoring and modeling: A new challenge for city-level ozone pollution control in the pearl river delta region

Ozone distribution and variation within the Planetary Boundary Layer (PBL) present challenges for air quality management. UAV-based ozone profile measurements offer advantages in terms of high vertical resolution throughout the PBL and flexibility. However, previous studies on vertical variation in the Pearl River Delta (PRD) region have rarely focused on measuring the vertical ozone variation during ozone pollution episodes. In this study, we integrated UAV-based monitoring, ground monitoring, and numerical modeling to investigate ozone variation, driving processes, and source regions of pollution episodic period. UAV-based observations during a 2021 ozone episode at rural areas in the PRD region revealed three ozone profiles: increasing, well-mixed, and decreasing with height. Morning profiles showed multiple layers influenced by meteorology, while peak ozone hours exhibited a well-mixed pattern. By integrating the validated numerical model, we found that chemical processes (CHEM) contributed positively to ozone episodes in both rural and urban scenarios, especially at the middle and upper PBL. Horizontal advection (HADV) significantly contributes to the episode in rural cases, while urban cases were significantly affected by vertical diffusion (VDIF). Backward trajectory and source apportionment analyses categorized PRD cities into upwind/non-upwind/local categories, showing ozone pollution originating from both upwind and non-upwind cities at different vertical levels. It is because wind shear influenced diverse source regions, and the transport channel for city-level ozone pollution exhibited daily and vertical changes. Moreover, it could also be contributed by the formed regional mixing ozone layer (ROM Layer) throughout the PBL during persistent ozone episodes, triggered by enhanced CHEM and significantly contributed by the VDIF. The ROM Layer at center cities, influencing ground-level ozone downwind through horizontal transport and vertical exchange. Considering the complex three-dimensional transport of ozone and the ROM Layer phenomenon, city-level management or regional co-control based on simple transport channels may be insufficient. Emissions control measures should cover all cities or target significant emitters to address regional ozone pollution.

Ozone pollution episodes and PBL height variation in the NYC urban and coastal areas during LISTOS 2019

In summer, frequent ozone (O3) episodes occur in New York City (NYC) and coastal areas along Long Island Sound (LIS) due to complex interplay of urban pollutants transport, land-sea breezes, and chemistry. The Long Island Sound Tropospheric Ozone Study (LISTOS) was carried out to address this issue; here we present an integrated analysis of the diurnal variation of planetary-boundary-layer height (PBLH) and O3 in the NYC urban and coastal area during LISTOS in summer 2019. A persistent O3 episode (July 28–31, 2019) is investigated which shows much higher O3 (90–120 ppb with 5-min average maximum) along the North-shore of Long Island (NLI) than the NYC urban and South-shore of Long Island (SLI). We evaluate the PBLH estimate with a multi-platform observation in the complex coastal environment, and compare the PBLH diurnal variation in the NYC urban to coastal areas. The results indicate lower PBLH in the mid-morning and noon in the NLI than the NYC urban area. With the simultaneously measured O3 and PBLH, the integrated O3 content or total content in the PBL defined as the O3 concentrations multiplied by PBLH show good consistency in the urban and NLI coast at noon on July 28–29, 2019. A dense O3 plume, rich in CO, aerosols, black carbon, HCHO and NOx appeared in the PBL as detected from the UMD Cessna research aircraft, satellite TROPOMI and ozonesonde; their coincidently large values imply the combined effects of urban plumes transport, lower PBLH and land-sea breezes in the NLI area. Finally, we evaluated the forecast of O3 and PBLH from the NOAA NAM-CMAQ (12 km grid) and WRF-Chem (1.3 km grid) models with the observations. Both models show good agreement with the observations at the NYC urban site; but at the NLI coastal site, the NAM-CMAQ model forecast indicates a timing bias for the maximum O3 at noon. These results provide insight into the impacts of the sea breeze and urban heat island on air quality.

Comparison of the ozone formation mechanisms and VOCs apportionment in different ozone pollution episodes in urban Beijing in 2019 and 2020: Insights for ozone pollution control strategies

Ground-level ozone (O3) pollution has been a tough issue in urban areas of China in the past decade. Clarifying the formation mechanisms of O3 and the sources of its precursors is necessary for the effective prevention of O3 pollution. In this study, a comparative analysis of O3 formation mechanisms and VOCs apportionment for five O3 pollution episodes was carried out at two urban sites (CRAES and CGZ) in Beijing in 2019 and 2020 by applying an observation-based modeling approach in order to obtain insights into O3 pollution control strategies. Results indicated that O3 pollution levels were generally more severe in 2019 than in 2020 during the observation periods. O3 formation at the two sites was both VOCs-limited on O3 polluted days and non-O3 polluted days. Stronger atmospheric oxidation capacity and ROx radicals cycling processes were found on O3 polluted days which could accelerate the local production of O3, and local photochemical production dominated the observed O3 concentrations at the two sites even on non-O3 polluted days. Emission reduction of VOCs should be a priority for mitigating O3 pollution, and alkenes and biogenic VOCs was the priority species at the CRAES and CGZ sites, respectively. Additionally, the reduction of oxygenated VOCs should also be important for the ozone control. Gasoline exhaust at the CRAES site, and solvent utilization and fuel evaporation at the CGZ site were main anthropogenic sources of VOCs. Therefore, local control measures should be further strengthened and differentiated control strategies of VOCs in the aspects of area, time, sources and species should be adopted in urban Beijing in the future. Overall, the findings of this study could provide a scientific understanding of the causes of O3 pollution and significant guidelines for formulating O3 control strategies from the perspective of different ozone pollution episodes in urban Beijing.

Investigation of the summer 2018 European ozone air pollution episodes using novel satellite data and modelling

Abstract. In the summer of 2018, Europe experienced an intense heatwave which coincided with several persistent large-scale ozone (O3) pollution episodes. Novel satellite data of lower-tropospheric column O3 from the Global Ozone Monitoring Experiment-2 (GOME-2) and Infrared Atmospheric Sounding Interferometer (IASI) on the MetOp satellite showed substantial enhancements in 2018 relative to other years since 2012. Surface observations also showed ozone enhancements across large regions of continental Europe in summer 2018 compared to 2017. Enhancements to surface temperature and the O3 precursor gases carbon monoxide and methanol in 2018 were co-retrieved from MetOp observations by the same scheme. This analysis was supported by the TOMCAT chemistry transport model (CTM) to investigate processes driving the observed O3 enhancements. Through several targeted sensitivity experiments we show that meteorological processes, and emissions to a secondary order, were important for controlling the elevated O3 concentrations at the surface. However, mid-tropospheric (∼ 500 hPa) O3 enhancements were dominated by meteorological processes. We find that contributions from stratospheric O3 intrusions ranged between 15 %–40 %. Analysis of back trajectories indicates that the import of O3-enriched air masses into Europe originated over the North Atlantic, substantially increasing O3 in the 500 hPa layer during summer 2018.

Characteristics, Sources, and Contributions to Ozone Formation of Ambient Volatile Organic Compounds in Huanggang, China

Based on the offline sampling data of volatile organic compounds (VOCs) and the simultaneous online measurements of conventional gaseous air pollutants and meteorological parameters in urban Huanggang, the volume fractions and component characteristics of VOCs were analyzed. The sources and ozone (O3) formation sensitivity of VOCs during severe ozone pollution episodes were analyzed using the positive matrix factorization (PMF) model and the photochemical box model coupled with master chemical mechanism (PBM-MCM), respectively. The results revealed that the average volume fractions of total volatile organic compounds were (21.57±3.13)×10-9, with higher volume fractions in winter and spring compared to those in summer and autumn. Among these, alkanes (49.9%) and alkenes (16.4%) accounted for the highest proportion. The PMF analysis results showed that fuel combustion (27.8%), vehicle emission (19.9%), solvent use (15.7%), industrial halogenated hydrocarbon emission (12.1%), chemical enterprise emission (10.5%), natural sources (7.8%), and diesel vehicle emission (6.2%) were the main sources of VOC emissions. Anthropogenic VOCs emitted by solvent use, fuel combustion, and chemical enterprises contributed significantly (60.9% in total) to generating O3, which indicates that these three types of anthropogenic sources should be controlled first when it comes to preventing and controlling ozone pollution. Further, the relative incremental reactivity (RIR) and empirical kinetic method approach (EKMA) revealed that O3 formation was in a VOCs-limited regime during the observation period in Huanggang, China. Furthermore, O3 formation was more sensitive to m-xylene, p-xylene, ethylene, 1-butene, and toluene; therefore, reducing these VOCs should be prioritized.

Rising frequency of ozone-favorable synoptic weather patterns contributes to 2015–2022 ozone increase in Guangzhou

Objective weather classification methods have been extensively applied to identify dominant ozone-favorable synoptic weather patterns (SWPs), however, the consistency of different classification methods is rarely examined. In this study, we apply two widely-used objective methods, the self-organizing map (SOM) and K-means clustering analysis, to derive ozone-favorable SWPs at four Chinese megacities in 2015–2022. We find that the two algorithms are largely consistent in recognizing dominant ozone-favorable SWPs for four Chinese megacities. In the case of classifying six SWPs, the derived circulation fields are highly similar with a spatial correlation of 0.99 between the two methods, and the difference in the mean frequency of each SWP is less than 7%. The six dominant ozone-favorable SWPs in Guangzhou are all characterized by anomaly higher radiation and temperature, lower cloud cover, relative humidity, and wind speed, and stronger subsidence compared to climatology mean. We find that during 2015–2022, the occurrence of ozone-favorable SWPs days increases significantly at a rate of 3.2 day/year, faster than the increases in the ozone exceedance days (3.0 day/year). The interannual variability between the occurrence of ozone-favorable SWPs and ozone exceedance days are generally consistent with a temporal correlation coefficient of 0.6. In particular, the significant increase in ozone-favorable SWPs in 2022, especially the Subtropical High type which typically occurs in September, is consistent with a long-lasting ozone pollution episode in Guangzhou during September 2022. Our results thus reveal that enhanced frequency of ozone-favorable SWPs plays an important role in the observed 2015–2022 ozone increase in Guangzhou.

Source apportionment and ozone formation mechanism of VOCs considering photochemical loss in Guangzhou, China

Understanding the sources and impact of volatile organic compounds (VOCs) on ozone formation is challenging when the traditional method does not account for their photochemical loss. In this study, online monitoring of 56 VOCs was carried out in summer and autumn during high ozone pollution episodes. The photochemical age method was used to evaluate the atmospheric chemical loss of VOCs and to analyze the effects on characteristics, sources, and ozone formation of VOC components. The initial concentrations during daytime were 5.12 ppbv and 4.49 ppbv higher than the observed concentrations in the summer and autumn, respectively. The positive matrix factorization (PMF) model identified 5 major emission sources. However, the omission of the chemical loss of VOCs led to underestimating the contributions of sources associated with highly reactive VOC components, such as those produced by biogenic emissions and solvent usage. Conversely it resulted in overestimating the contributions from VOC components with lower chemical activity such as liquefied petroleum gas (LPG) usage, vehicle emissions, and gasoline evaporation. Furthermore, the estimation of ozone formation may be underestimated when the atmospheric photochemical loss is not taken into account. The ozone formation potential (OFP) method and propylene-equivalent concentration method both underestimated ozone formation by 53.24 ppbv and 47.25 ppbc, respectively, in the summer, and by 40.34 ppbv and 26.37 ppbc, respectively, in the autumn. The determination of the ozone formation regime based on VOC chemical loss was more acceptable. In the summer, the ozone formation regime changed from the VOC-limited regime to the VOC-NOx transition regime, while in the autumn, the ozone formation regime changed from the strong VOC-limited regime to the weak VOC-limited regime. To obtain more thorough and precise conclusions, further monitoring and analysis studies will be conducted in the near future on a wider variety of VOC species such as oxygenated VOCs (OVOCs).

Measurement report: MAX-DOAS measurements characterise Central London ozone pollution episodes during 2022 heatwaves

Abstract. Heatwaves are a substantial health threat in the UK, exacerbated by co-occurrence of ozone pollution episodes. Here we report on the first use of retrieved vertical profiles of nitrogen dioxide (NO2) and formaldehyde (HCHO) over Central London from a newly installed multi-axis differential optical absorption spectroscopy (MAX-DOAS) instrument coincident with two of three heatwaves for the hottest summer on record. We evaluate space-based sensor observations routinely used to quantify temporal changes in air pollution and precursor emissions over London. Collocated daily mean tropospheric column densities from the high-spatial-resolution space-based TROPOspheric Monitoring Instrument (TROPOMI) and MAX-DOAS, after accounting for differences in vertical sensitivities, are temporally consistent for NO2 and HCHO (both R = 0.71). TROPOMI NO2 is 27 %–31 % less than MAX-DOAS NO2, as expected from horizontal dilution of NO2 by TROPOMI pixels in polluted cities. TROPOMI HCHO is 20 % more than MAX-DOAS HCHO, greater than differences in past validation studies but within the range of systematic errors in the MAX-DOAS retrieval. The MAX-DOAS near-surface (0–110 m) retrievals have similar day-to-day and hourly variability to the surface sites for comparison of NO2 (R ≥ 0.7) and for MAX-DOAS HCHO versus surface site isoprene (R ≥ 0.7) that oxidises to HCHO in prompt and high yields. Daytime ozone production, diagnosed with MAX-DOAS HCHO-to-NO2 tropospheric vertical column ratios, is mostly limited by availability of volatile organic compounds (VOCs), except on heatwave days. Temperature-dependent biogenic VOC emissions of isoprene increase exponentially, resulting in ozone concentrations that exceed the regulatory standard for ozone and cause non-compliance at urban background sites in Central London. Locations in Central London heavily influenced by traffic remain in compliance, but this is likely to change with stricter controls on vehicle emissions of NOx and higher likelihood of heatwave frequency, severity, and persistence due to anthropogenic climate change.

Observations and explicit modeling of summer and autumn ozone formation in urban Beijing: Identification of key precursor species and sources

Due to the complexity and nonlinearity of the ozone (O3) production, it is vital to understand the detailed knowledge of ozone–precursor relationship for the formulation of effective mitigation of surface ozone pollution. In this study, continuous measurements of O3, volatile organic compounds (VOCs), and related parameters were conducted at an urban site of Beijing in the summer and autumn of 2019. The photochemical box model contained the Master Chemical Mechanism (MCMv3.3.1) was used to reveal the detailed information on the photochemical O3 formation. Results show that the average concentration of total VOCs (TVOC) was 31.2 ± 10.7 ppb and 37.8 ± 18.9 ppb during the summer and autumn campaign, respectively, with the largest contribution from alkanes in both seasons, which mainly originated from liquefied petroleum gas (LPG) usage (20.2%–22.6%), gasoline vehicular exhaust (21.0%–21.6%), diesel vehicular exhaust (18.1%–18.3%), solvent usage (20.4%–24.1%), and fuel evaporation (16.4%–17.4%) that identified by positive matrix factorization (PMF) model. Heavy ozone pollution episodes were observed and the net local O3 production rate during summer (EP1) and autumn (EP2) pollution episode was 9.87 ± 0.62 ppbv h−1, and 9.44 ± 1.18 ppbv h−1, respectively, which was both dominated by the reaction between HO2 with NO. The analysis of relative incremental reactivity (RIR) and O3-NOx-VOC isopleth shows that ozone formation was VOC-limited in urban Beijing, with alkenes and aromatics contributed the most to O3 formation in summer and autumn, respectively. In addition, modellings for various emission reduction scenarios were carried out, indicating the reduction of gasoline vehicles emissions in summer and both reduction of gasoline vehicles and solvent usage emissions in autumn is the best measures to efficiently reduce O3 pollution. These results improved our understanding of O3 precursors and their impact on ozone production and provided a more targeted reference for controlling ozone pollution in Beijing.

Uptake of ozone by allergenic pollen grains

Ozone exacerbates allergy symptoms to certain pollens. The molecular mechanisms by which ozone affects pollen grains (PGs) and allergies are not fully understood, especially as the effects of pollutants may vary depending on the type of pollen. In this work, pollens of 22 different taxa were exposed under laboratory conditions to ozone (100 ppb) to quantify the ozone uptake by the PGs. The ozone uptake was highly variable among the 22 taxa tested. The highest ozone uptake per PG was measured on Acer negundo PGs (2.5 ± 0.2 pg∙PG−1). On average, tree pollens captured significantly more ozone than herbaceous pollens (average values of 0.5 and 0.02 pg∙PG−1, respectively). No single parameter (such as the number of apertures, pollen season, pollen size, or lipid fraction) could predict a pollen's ability to take up ozone. Lipids seem to act as a barrier to ozone uptake and play a protective role for some taxa. After inhalation of PGs, pollen-transported ozone could be transferred to mucous membranes and exacerbate symptoms through oxidative stress and local inflammation. Although the amount of ozone transported is small in absolute terms, it is significant compared to the antioxidant capacity of nasal mucus at a microscale. This mechanism of pollen-induced oxidative stress could explain the aggravation of allergic symptoms during ozone pollution episodes.

Chemical Characteristics and Source Apportionment for VOCs During the Ozone Pollution Episodes and Non-ozone Pollution Periods in Qingdao

The ambient concentration of ozone is high in Qingdao, and ozone pollution episodes occur frequently in summer. The refined source apportionment of ambient volatile organic compounds (VOCs) and their ozone formation potential (OFP) during ozone pollution episodes and non-ozone pollution periods can play an important role in effectively reducing air ozone pollution in coastal cities and continuously improving ambient air quality. Therefore, this study applied the online VOCs monitoring data with hourly resolution in summer (from June to August) in 2020 in Qingdao to analyze the chemical characteristics of ambient VOCs during the ozone pollution episodes and non-ozone pollution periods and conducted the refined source apportionment of ambient VOCs and their OFP using a positive matrix factorization (PMF) model. The results showed that the average mass concentration of ambient VOCs in Qingdao in summer was 93.8 μg·m-3, and compared with that during the non-ozone pollution period, the mass concentration of ambient VOCs during the ozone pollution episodes increased by 49.3%, and the mass concentration of aromatic hydrocarbons increased by 59.7%. The total OFP of ambient VOCs in summer was 246.3 μg·m-3. Compared with that in the non-ozone pollution period, the total OFP of ambient VOCs in the ozone pollution episodes increased by 43.1%; that of alkanes increased the most, reaching 58.8%. M-ethyltoluene and 2,3-dimethylpentane were the species with the largest increase in OFP and its proportion during the ozone pollution episodes. The main contributors of ambient VOCs in Qingdao in summer were diesel vehicles (11.2%), solvent use (4.7%), liquefied petroleum gas and natural gas (LPG/NG) (27.5%), gasoline vehicles (8.9%), gasoline volatilization (26.6%), emissions of combustion- and petrochemical-related enterprises (16.4%), and plant emissions (4.8%). Compared with that in the non-ozone pollution period, the contribution concentration of LPG/NG in the ozone pollution episodes increased by 16.4 μg·m-3, which was the source category with the largest increase. The contribution concentration of plant emissions increased by 88.6% in the ozone pollution episodes, which was the source category with the highest increase rate. In addition, emissions from combustion- and petrochemical-related enterprises were the largest contributor to the OFP of ambient VOCs in summer in Qingdao, with its OFP and contribution proportion being 38.0 μg·m-3and 24.5%, respectively, followed by that of LPG/NG and gasoline volatilization. Compared with the non-ozone pollution period, the total contributions of LPG/NG, gasoline volatilization, and solvent use to the increase in OFP for ambient VOCs in the ozone pollution episodes were 74.1%, which were the main contribution source categories.

Ambient VOCs Characteristics and Reactivity During O3 Pollution in Autumn in Urban Beijing

In order to understand the effect of volatile organic compounds (VOCs) on ozone pollution, the concentrations, chemical composition variations, and ozone formation potential (OFP) were studied under different O3 concentrations, using high-resolution online monitoring data obtained in the urban site of Beijing in autumn of 2019. The results showed that the average concentration of VOCs was (22.22±10.10)×10-9, with the largest contribution of VOCs from alkanes (55.65%), followed by that of oxygenated volatile organic compounds (OVOCs) (16.23%) and alkenes (8.13%). Three ozone pollution episodes were captured during the observation period. The average concentration of VOCs on pollution days was (26.22±12.52)×10-9, which was 60.17%higher than that on clear days (16.37±7.19)×10-9. The value of ozone formation potential (OFP) on pollution days was 113.63 μg·m-3, which was 56.55%higher than that on clear days. The contributions of OVOCs and aromatics to OFP on pollution days increased by 6.51%and 1.55%, respectively, whereas that of alkenes declined (8.72%). The ratios of toluene to benzene (T/B) and benzene, toluene, and ethylbenzene (B:T:E) were 1.55 and 0.36:0.55:0.09, respectively, indicating that vehicle exhaust had significant effects on VOCs in autumn in urban Beijing. The back-trajectory results indicated a high contribution of southern air masses to atmospheric VOCs variations in autumn in urban Beijing.

Characteristics, sources and health risk assessment of atmospheric carbonyls during multiple ozone pollution episodes in urban Beijing: Insights into control strategies

Carbonyls have attracted continuous attention due to their critical roles in atmospheric chemistry and their potential hazards to the ecological environment and human health. In this study, atmospheric carbonyls were measured during several ground-level-ozone (O3) pollution episodes at three urban sites (CRAES, IEP and BJUT) in Beijing in 2019 and 2020. Comparative analysis revealed that the carbonyl concentrations were 20.25 ± 6.91 ppb and 13.43 ± 5.13 ppb in 2019 and 2020 in Beijing, respectively, with a significant spatial trend from north to south, and carbonyl levels in urban Beijing were in an upper-intermediate range in China, and higher than those in other countries reported in the literature. A particularly noteworthy phenomenon is the consistency of carbonyl concentrations with variations in O3 concentrations. On O3 polluted days, the carbonyl concentrations were 1.3–1.5 times higher than those on non-O3 polluted days. Secondary formation contributed more to formaldehyde (FA) and acetaldehyde (AA) on O3 polluted days, while the anthropogenic emissions were more significant for acetone (AC) on non-O3 polluted days. Vehicle exhaust and solvent utilization were the main primary contributors to carbonyls. Due to reduced anthropogenic emissions caused by the COVID-19 lockdown and the “Program for Controlling Volatile Organic Compounds in 2020” in China, the contributions of primary emissions to carbonyls decreased in 2020 in Beijing. Human cancer risks to exposed populations from FA and AA increased with elevated O3 levels, and the risks still remained on non-O3 polluted days. The residents around the BJUT site might experience relatively higher human cancer risks than those around the other two sites. The findings in this study confirmed that atmospheric carbonyl pollution and its potential human health hazards cannot be ignored in urban Beijing; therefore, more strict control strategies for atmospheric carbonyls are urgently needed to better protect human health in Beijing in the future.