O3 Precursors Research Articles

What controls ozone sensitivity in the upper tropical troposphere?

Abstract. Ozone is an important contributor to the radiative energy budget of the upper troposphere (UT). Therefore, observing and understanding the processes contributing to ozone production are important for monitoring the progression of climate change. Nitrogen oxides (NOx ≡ NO + NO2) and volatile organic compounds (VOCs) are two main tropospheric precursors to ozone formation. Depending on their abundances, ozone production can be sensitive to changes in either of these two precursors. Here, we focus on processes contributing to ozone chemistry in the upper tropical troposphere between 30∘ S and 30∘ N latitude, where changes in ozone have a relatively large impact on anthropogenic radiative forcing. Based on modeled trace gas mixing ratios and meteorological parameters simulated by the ECHAM5/MESSy2 Atmospheric Chemistry (EMAC) general circulation model, we analyze a variety of commonly applied metrics including ozone production rates (P(O3)), the formaldehyde (HCHO) to NO2 ratio and the share of methyl peroxy radicals (CH3O2) forming HCHO (α(CH3O2)) for their ability to describe the chemical regime. We show that the distribution of trace gases in the tropical UT is strongly influenced by the varying locations of deep convection throughout the year, and we observe peak values for NOx and P(O3) over the continental areas of South America and Africa where lightning is frequent. We find that P(O3) and its response to NO is unsuitable for determining the dominant regime in the upper troposphere. Instead, α(CH3O2) and the HCHO/NO2 ratio in combination with ambient NO levels perform well as metrics to indicate whether NOx or VOC sensitivity is prevalent. We show that effectively only the knowledge of the availability of NO and HO2 is required to adequately represent O3 precursors and its sensitivity towards them. A sensitivity study with halving, doubling and excluding lightning NOx demonstrates that lightning and its distribution in the tropics are the major determinants of the chemical regimes and ozone formation in the upper tropical troposphere.

Effects of VOC emissions from chemical industrial parks on regional O3-PM2.5 compound pollution in the Yangtze River Delta

Ozone (O3) and fine particulate matter (PM2.5) compound pollution has emerged as a primary form of air pollution in Chinese urban. Volatile organic compounds (VOCs), as common precursors of O3 and PM2.5, play a significant role in air pollution control. Chemical industrial parks (CIPs) are crucial emission sources of VOCs and have garnered significant attention. This study focused on 142 CIPs located in the Yangtze River Delta (YRD) to investigate the characteristics of VOC emissions from CIPs and their impact on O3-PM2.5 compound pollution, considering the enhanced atmospheric oxidation capacity (AOC). The Comprehensive Air Quality Model with Extensions (CAMx) model was employed for this analysis. The results show that VOC emissions from CIPs contributed significantly to regional O3 and secondary organic aerosol (SOA), accounting for 17.1 % and 18.18 % of the anthropogenic sources, respectively. Regions exhibiting the highest contributions were located along the Hangzhou Bay. Compared with 2014, an elevation in the contribution of VOC emissions from CIPs to the annual average concentrations of MDA8 O3 and SOA in the YRD in 2017 by 0.069 μg/m3 and 0.007 μg/m3, respectively. During episodes of compound pollution, the concentration of atmospheric oxidant (HOx + NO3) was 28.65 % higher than during clean days, and significant positive correlations were observed between hydrogen oxygen radicals (HOx) and maximum daily 8-h average (MDA8 O3) as well as between HOx and SOA, exhibiting correlation coefficients of 0.86 and 0.48, respectively. Effective control measures for VOC emissions, particularly from the pharmaceutical and petrochemical industry parks located along Hangzhou Bay, are essential in curtailing the production rate of HOx and in regulating AOC levels in the YRD. Maintaining the daily average HOx concentration below 10 ppt would be a valuable strategy in achieving coordinated control of O3 and SOA, thus aiding in the alleviation of O3-PM2.5 compound pollution in the YRD.

Examining the Summertime Ozone Formation Regime in Southeast Michigan Using MOOSE Ground‐Based HCHO/NO2 Measurements and F0AM Box Model

AbstractAmbient ozone (O3) concentrations in Southeast Michigan (SEMI) can exceed the U.S. National Ambient Air Quality Standard. Despite past efforts to measure O3 precursors and elucidate reaction mechanisms, changing emission patterns and atmospheric composition in SEMI warrant new measurements and updated mechanisms to understand the causes of observed O3 exceedances. In this study, we examine the chemical drivers of O3 exceedances in SEMI, based on the Phase I MOOSE (Michigan‐Ontario Ozone Source Experiment) field study performed during May to June 2021. A zero‐dimensional (0‐D) box model is constrained with measurement data of meteorology and trace gas concentrations. Box model sensitivity simulations suggest that the formaldehyde to nitrogen dioxide ratio (HCHO/NO2) for the transition between the volatile organic compounds (VOCs)‐ and nitrogen oxides (NOx)‐limited O3 production regimes is 3.0 ± 0.3 in SEMI. The midday (12:00–16:00) averaged HCHO/NO2 ratio during the MOOSE Phase I study is 1.62 ± 1.03, suggesting that O3 production in SEMI is limited by VOC emissions. This finding implies that imposing stricter regulations on VOC emissions should be prioritized for the SEMI O3 nonattainment area. This study, through its use of ground‐based HCHO/NO2 ratios and box modeling to assess O3‐VOC‐NOx sensitivities, has significant implications for air quality policy and the design of effective O3 pollution control strategies, especially in O3 nonattainment areas.

Exploring the amplified role of HCHO in the formation of HMS and O3 during the co-occurring PM2.5 and O3 pollution in a coastal city of southeast China

Abstract. To develop effective strategies for controlling both PM2.5 and O3 levels, it is crucial to understand their synergistic mechanisms and key precursors and the atmospheric physiochemical processes involved. In this study, a wintertime co-occurring O3 and PM2.5 pollution event in a coastal city in southeast China was investigated based on high-time-resolution measurements of criteria air pollutants and chemical compositions of PM2.5, and O3 precursors, such as NOx, HCHO, and volatile organic compounds (VOCs). The results of this study revealed the characteristics of positively correlated PM2.5 and MDA8 O3 concentrations, and an increase in atmospheric oxidation capacity (AOC) during the cold seasons. Strong correlations (R2= 0.415–0.477) between HCHO, Fe, Mn, and sulfate concentrations were observed, suggesting the influence of catalyzed oxidation processes in the coastal city. Through an observation-based model (OBM) analysis coupled with the Regional Atmospheric Chemistry Mechanism, version 2 (RACM2) and the Chemical Aqueous-Phase Radical Mechanism, version 3.0 (CAPRAM 3.0), we found that high concentrations of precursors (SO2 and HCHO), high relative humidity, and moderately acidic pH conditions enhanced the heterogeneous formation of hydroxymethanesulfonate (HMS) in PM2.5. Furthermore, by employing an OBM coupled to the Master Chemical Mechanism (OBM-MCM), we verified that disabling the HCHO mechanism could decrease daytime net O3 production rates by reducing the production rates of HO2 + NO. These results were consistent with the daily values of AOC, OH, HO2, and RO2 concentrations. This study contributes to a better understanding of the significance of HCHO in photochemical reactions and the formation of HMS in a coastal city.

Large-scale land-sea interactions extend ozone pollution duration in coastal cities along northern China

Land-sea atmosphere interaction (LSAI) is one of the important processes affecting ozone (O3) pollution in coastal areas. The effects of small-scale LSAIs like sea-land breezes have been widely studied. However, it is not fully clear how and to what extent the large-scale LSAIs affect O3 pollution. Here we explored an O3 episode to illuminate the role of large-scale LSAIs in O3 pollution over the Bohai–Yellow Seas and adjacent areas through observations and model simulations. The results show that the northern Bohai Sea's coastal region, influenced by the Mongolian High, initially experienced a typical unimodal diurnal O3 variation for three days, when O3 precursors from Beijing–Tianjin–Hebei, Shandong, and Northeast China were transported to the Bohai–Yellow Seas. Photochemical reactions generated O3 within marine air masses, causing higher O3 levels over the seas than coastal regions. As the Mongolian High shifted eastward and expanded, southerly winds on its western edge transported O3-rich marine air masses toward the coast, prolonging pollution for an additional three days and weakening diurnal variations. Subsequently, emissions from the Korean Peninsula and marine shipping significantly affected O3 levels in the northern Bohai Sea (10.7% and 13.7%, respectively). Notably, Shandong's emissions played a substantial role in both phases (27.5% and 26.1%, respectively). These findings underscore the substantial impact of large-scale LSAIs driven by the Mongolian High on O3 formation and pollution duration in coastal cities. This insight helps understand and manage O3 pollution in northern Bohai Sea cities and broadly applies to temperate coastal cities worldwide.

Space-Based Observations of Ozone Precursors within California Wildfire Plumes and the Impacts on Ozone-NOx-VOC Chemistry.

The frequency of wildfires in the western United States has escalated in recent decades. Here we examine the impacts of wildfires on ground-level ozone (O3) precursors and the O3-NOx-VOC chemistry from the source to downwind urban areas. We use satellite retrievals of nitrogen dioxide (NO2) and formaldehyde (HCHO, an indicator of VOC) from the Tropospheric Monitoring Instrument (TROPOMI) to track the evolution of O3 precursors from wildfires over California from 2018 to 2020. We improved these satellite retrievals by updating the a priori profiles and explicitly accounting for the effects of smoke aerosols. TROPOMI observations reveal that the extensive and intense fire smoke in 2020 led to an overall increase in statewide annual average HCHO and NO2 columns by 16% and 9%. The increase in the level of NO2 offsets the anthropogenic NOx emission reduction from the COVID-19 lockdown. The enhancement of NO2 within fire plumes is concentrated near the regions actively burning, whereas the enhancement of HCHO is far-reaching, extending from the source regions to urban areas downwind due to the secondary production of HCHO from longer-lived VOCs such as ethene. Consequently, a larger increase in NOx occurs in NOx-limited source regions, while a greater increase in HCHO occurs in VOC-limited urban areas, both contributing to more efficient O3 production.

Simulations of winter ozone in the Upper Green River basin, Wyoming, using WRF-Chem

Abstract. In the Upper Green River basin (UGRB) of Wyoming and the Uintah Basin of Utah, strong wintertime ozone (O3) formation episodes leading to O3 mixing ratios occasionally exceeding 70 parts per billion (ppb) have been observed over the last 2 decades. Wintertime O3 events in the UGRB were first observed in 2005 and since then have continued to be observed intermittently when meteorological conditions are favorable, despite significant efforts to reduce emissions from oil and natural gas extraction and production. While O3 formation has been successfully simulated using observed volatile organic compound (VOC) and nitrogen oxide (NOx) mixing ratios, successful simulation of these wintertime episodes using emission inventories in a 3-D photochemical model has remained elusive. An accurate 3-D photochemical model driven by an emission inventory is critical to understanding the spatial extent of high-O3 events and which emission sources have the most impact on O3 formation. In the winter of 2016/17 (December 2016–March 2017) several high-O3 events were observed with 1 h mixing ratios exceeding 70 ppb. This study uses the Weather Research and Forecasting model coupled with Chemistry (WRF-Chem) to simulate one of the high-O3 events observed in the UGRB during March 2017. The WRF-Chem simulations were carried out using the 2014 edition of the Environmental Protection Agency National Emissions Inventory (EPA NEI2014v2), which, unlike previous versions, includes estimates of emissions from non-point oil and gas production sources. Simulations were carried out with two different chemical mechanisms: the Model for Ozone and Related Chemical Tracers (MOZART) and the Regional Atmospheric Chemistry Mechanism (RACM), and the results were compared with data from seven weather and air quality monitoring stations in the UGRB operated by the Wyoming Department of Environmental Quality (WYDEQ). The simulated meteorology compared favorably to observations with regard to temperature inversions, surface temperature, and wind speeds. Notably, because of snow cover present in the basin, the photolysis surface albedo had to be modified to predict O3 in excess of 70 ppb, although the models were relatively insensitive to the exact photolysis albedo if it was over 0.65. O3 precursors, i.e., NOx and VOCs, are predicted similarly in simulations with both chemical mechanisms, but simulated VOC mixing ratios are a factor of 6 or more lower than the observations, while NOx is also underpredicted but to a lesser degree. Sensitivity simulations revealed that increasing NOx and VOC emissions to match observations produced slightly more O3 compared to baseline simulations, but an additional sensitivity simulation with doubled NOx emissions resulted in a considerable increase in O3 formation. These results suggest that O3 formation in the basin is most sensitive to NOx emissions.

Long-term exposure to ambient ozone and cardiovascular diseases: Evidence from two national cohort studies in China

IntroductionThe health effects of ambient ozone have been investigated in many previous studies. However, the effects of long-term exposure to ambient ozone on the incidence of cardiovascular disease (CVD) remain inconclusive. ObjectivesTo estimate the associations of long-term exposure to maximum daily 8-hours average ozone (MDA8 O3) with the incidence of total CVD, heart disease, hypertension, and stroke. MethodsThis was a prospective cohort study, and the data was obtained from the China Health and Retirement Longitudinal Survey (CHARLS) implemented during 2011–2018 and the China Family Panel Studies (CFPS) implemented during 2010–2018. We applied a Cox proportional hazards regression model to evaluate the associations of MDA8 O3 with total CVD, heart disease, hypertension, and stroke risks, and the corresponding population-attributable fractions (PAF) attributable to MDA8 O3 were also calculated. All analyses were conducted by R software. ResultsThe mean MDA8 O3 concertation of all included participants in the CHARLS and CFPS were 51.03 part per billion (ppb) and 51.15 ppb, respectively. In the CHARLS including 18,177 participants, each 10 ppb increment in MDA8 O3 concentration was associated with a 31% increase [hazard ratio (HR) = 1.31, 95% confidence interval (CI): 1.22–1.42] in the risk of incident heart disease, and the corresponding population-attributable fractions (PAF) was 13.79% [10.12%-17.32%]. In the CFPS including 30,226 participants, each 10 ppb increment in MDA8 O3 concentration was associated with an increase in the risk of incident total CVD (1.07 [1.02–1.13]), and hypertension (1.10 [1.03–1.18]). The PAFs of total CVD, and hypertension attributable to MDA8 O3 were 3.53% [0.82%-6.16%], and 5.11% [1.73%-8.38%], respectively. Stratified analyses showed greater associations in males, urban areas, and Southern China. ConclusionsLong-term exposure to MDA8 O3 may increase the incidence of CVD. Therefore, the policies that control O3 and related precursors are persistently needed.

Oxidation capacity changes in the atmosphere of large urban areas in Europe: Modelling and experimental campaigns in atmospheric simulation chambers

Air pollution is a major concern for human health and the environment. Consequently, environmental standards have become stricter to improve air quality. Thanks to this, the ambient levels of O3 precursors such as VOCs and NOX have decreased. However, O3 levels in Europe, especially during winter, have increased, potentially impacting on atmospheric oxidation capacity and the associated chemistry of tropospheric oxidants. In this work, we focus on recent changes in the oxidation capacity of urban atmospheres. The study is conducted with the results of the CMAQ modelling system with a regional resolution with 12 × 12 km2 across the entire European continent for the winter (January) and summer (July) of 2007 and 2015. The 2015 meteorological data is used for both years to emphasise emission changes during the studied period. We scrutinise the changes in ambient concentration levels of the main tropospheric oxidants (O3 and HOX radicals) in five representative cities, Valencia, Madrid, Milan, Berlin, and The Hague. The enhanced O3 formation in winter seems to be due to the low VOC/NOX ratio, while the opposite trend in summer may be related to a relatively high ratio. Additionally, photooxidation experiments are carried out in the EUPHORE chambers to study the effect of changes in NOX concentration and NO/NO2 ratio on the variation of the given oxidants at constant VOCs concentrations. For the baseline experiments, two scenarios are selected based on the model results of 2015: two representative winter and summer days of low and high pollution in Berlin and Madrid, respectively. The role of VOC/NOX and NO/NO2 ratios on atmospheric reactivity is discussed. As a result, it is first suggested that further decreases in ambient NOX levels are required to reduce ambient O3 levels. Moreover, additional factors should be considered when designing local-specific emission abatement strategies.

Photochemistry in the urban agglomeration along the coastline of southeastern China: Pollution mechanism and control implication

The concentrations of ground-level ozone (O3) in China have undergone a rapid increase in recent years, resulting in adverse impacts on the air quality and climate change. However, limited research has been conducted on the coastal urban agglomerations with increasingly serious O3 pollution. Therefore, in order to better understand in situ photochemistry, comprehensive field observations of O3 and its precursors, coupled with the model simulation, were conducted in autumn of 2019 at six sites in an urban agglomeration along the coastline of southeastern China. Results indicated that O3 pollution in the southern part of the urban agglomeration was more severe than that in the northern part, due to higher levels of O3 precursors and stronger atmospheric oxidation capacity (AOC) in the southern regions. Oxygenated volatile organic compounds (OVOCs), NO2, and CO dominated the total OH reactivity, and the site-average daytime Ox (O3 + NO2) increments correlated well (R2 = 0.94) with the total OH reactivity of CO and VOCs at these sites except for Quanzhou, where industrial emissions (35.1 %) and solvent usages (33.7 %) dominated the VOC sources. However, vehicle exhausts (31.1 %) were the most predominant contributors to the VOC sources at other sites. The results of model simulations showed that net O3 formation rates were larger at the southern sites. Furthermore, O3 production was mainly controlled by VOCs at most sites, but co-limited by VOCs and NOx at Quanzhou. The most significant VOC groups contributing to O3 formation were aromatics and alkenes, with m/p-xylene, toluene, propene, and ethene being the main contributors at these sites. This study offers a more comprehensive understanding of the characteristics and formation of photochemical pollutions on the scale of the urban areas, indicating the critical need to reduce VOC emissions as a means of mitigating their photochemical effects.

Response of PM2.5 and O3 to Emission Reductions in Nanjing Based on Random Forest Algorithm

High levels of fine particulate matter (PM2.5) and ozone (O3) in ambient air affect climate change and also endanger human health and ecosystems. Air pollution in Nanjing has been improving since the implementation of the "Air Pollution Prevention and Control Action Plan" in 2013. However, Nanjing still faces PM2.5 and O3 pollution. Evaluating the response of pollutant concentrations to the reductions in precursor emissions is helpful to obtain effective strategies of emission reduction to improve pollution levels. The sensitive simulations of emission perturbation in atmospheric chemistry models directly demonstrate the response of pollution to the reductions in emissions. Nevertheless, these sensitive simulations are limited in computing time and resources. The random forest algorithm was trained by using the simulation results of the atmospheric chemical transport model (GEOS-Chem) in 2015. The changes in daily PM2.5 and daily maximum eight-hour O3 (MDA8 O3) concentrations in Nanjing in 2019 were efficiently predicted under different reduction scenarios of anthropogenic emissions. The simulations showed that the seasonal average of ρ(PM2.5) in Nanjing would decrease by 2-4 μg·m-3 with the reduction in anthropogenic emissions of 10% in 2019 in China. In the case of controlling only local emissions in Nanjing, the concentrations of PM2.5 in Nanjing decreased significantly without local anthropogenic emissions. Additionally, the simulations showed that the annual average of ρ(PM2.5) in Nanjing could be lower than the national secondary limit (35 μg·m-3) when the anthropogenic emission reduction in China was higher than 20% in 2019. For ozone, the equal proportional emission reductions in nitrogen oxides (NOx) and volatile organic pollutants (VOCs) of O3 precursors in China likely led to the increase in seasonal average concentrations of O3 in Nanjing. For the proportional reduction of anthropogenic emissions by 10%-50% in China, the seasonal average of ρ(MDA8 O3) in Nanjing in 2019 would increase by 1-3 μg·m-3 in spring, 1-4 μg·m-3 in autumn, and 3-11 μg·m-3 in winter, respectively, compared with that in the base simulation. With the reduction in anthropogenic NOx emission by 10% and VOCs by 20%, the seasonal average of ρ(MDA8 O3) in Nanjing would decrease by 3-6 μg·m-3. On this basis, further increasing the proportion (30%) of VOCs emission reduction could reduce the annual average of ρ(MDA8 O3) in Nanjing by 7 μg·m-3. However, the annual average of ρ(MDA8 O3) of Nanjing in 2019 increased by 1 μg·m-3, with the local emission reduction of NOx by 10% and VOCs by 30%. Therefore, this showed that the key to alleviate ozone pollution in Nanjing is a reasonable control ratio of ozone precursor emissions and the implementation of regional joint prevention and control. In order to effectively reduce the O3 pollution in Nanjing, the emission reduction ratio of NOx and VOCs in China should be less than 1:2. The response of pollutant concentrations to reductions in precursor emissions were efficiently obtained by the random forest algorithm and GEOS-Chem model. The simulations would provide the scientific basis for the emission control strategy to alleviate air pollution.

Impacts of Synoptic Patterns and Meteorological Factors on Distribution Trends of Ozone in Southeast China During 2015–2020

AbstractSurface ozone (O3) pollution under global climate change has become one of the top environmental issues. In this study, we focused on the coastal region in Southeast China with relatively low O3 precursor's emissions and complicated synoptic conditions, where the O3 trends and meteorological contributions remain unclear. An increasing trend of O3 concentrations in the cities (0.3–4.6 μg m−3 yr−1) from 2015 to 2020 was observed. Twenty‐three synoptic patterns were clustered based on weather typing method, in which cyclone‐related types and southwesterly type were generally associated with low O3 concentrations, and high O3 levels occurred with anticyclone‐related types. Considering both frequency and intensity of synoptic patterns, reconstructed O3 series captured 46.0%–58.3% of the observed variability. Using Kolmogorov‐Zurbenko filter, an increasing trend of long‐term O3 was found. By implementing the multiple linear regression model between O3 concentrations and meteorological factors, the meteorological contributions to O3 variabilities (44.7%–66.1%) were quantified. The results indicated the meteorological conditions were particularly important in O3 pollution with the reductions of O3 precursor's emissions, among which relative humidity, boundary layer height, solar radiation along with low cloud cover were proved to play important roles. The weakening southwest winds along with more anti‐cyclone systems under climate change could increase surface O3. This study elucidated the crucial meteorological drivers on the O3 variability in relatively clean areas and implied the challenges for local governments to mitigate O3 pollution under global climate change.

Synergistic generation mechanisms of SOA and ozone from the photochemical oxidation of 1,3,5-trimethylbenzene: Influence of precursors ratio, temperature and radiation intensity

Aromatic hydrocarbons (AHs) are important anthropogenic precursors for both secondary organic aerosol (SOA) and ozone (O3) in urban areas. Knowledge about the synergistic processes and influence mechanisms of SOA and O3 during the photochemical oxidation of AHs is still relatively limited. In this study, the synergistic formation processes of SOA and O3 through the photochemical reactions of a representative AHs (1,3,5-trimethylbenzene, 135TMB) under different initial volatile organic compound/nitrogen oxides ([VOC]/[NOX]) ratios, temperatures and radiation intensities were investigated. The results showed that temperature and radiation significantly affected the reaction products and yields: the O3 production rates under high temperatures and radiation were greater than those under low temperatures and radiation, whereas the mass concentrations and yields of SOA under low temperatures and radiation were much higher than those under high temperatures and radiation. It was also found that the SOA yield increased with increasing NOX concentration within a specific initial [135TMB]/[NOX] ratio, but it decreased with increasing NOX concentration beyond a specific initial [135TMB]/[NOX] ratio. In addition, the concentrations of SOA and O3 in all the experiments increased simultaneously regardless of low temperatures or high temperatures. From these phenomena, it can be inferred that appropriate strategies for O3 precursor abatement can simultaneously reduce the concentration of SOA, which means that the coordinated control of fine particles and O3 could be achieved by taking coordinated emission reduction measures for VOCs and NOX precursors. The analysis of the organic components revealed that intramolecular hydrogen transfer occurred in some reactions in 135TMB photooxidation, and low-volatility and high-oxidative state organics were formed. The master chemical mechanism (MCM) results showed that the existing MCM mechanism does not yet fully meet the need to simulate the atmospheric photochemical reaction processes of 135TMB in the real atmosphere in China, and a localized MCM mechanism needs to be developed in the future.

Assessment of rice yield and economic losses caused by ground-level O3 exposure in the Mekong delta region, Vietnam

The Lower Mekong Delta region (LMD) accounts for 90% of Vietnam's rice exports; however, the air quality in the LMD is remarkably reduced by ground-level ozone (O3) pollution. This study aimed to quantify the relative yield and economic value losses in rice-growing crop seasons affected by ground-level O3 concentrations across the LMD. The results of this study can serve as a basis for extensive assessments for the following years and support environmental managers to propose control measures of O3 precursor emissions (NOx and VOCs) from man-made sectors, as well as build protective solutions for rice farming in LMD. Two ground-level O3 exposure metrics of M7 and AOT40 reflecting ground-level O3 pollution impacts, combined with the model of exposure-relative yield relationship (or surface O3-crop models), were used to assess losses of crop production (CPL) and economic cost losses (ECL) caused by rice crop yield reductions. For the M7 metric of ground-level O3 exposure, the average value was 14.746 ppbV, with levels ranging from 13.959 ppbV to 15.502 ppbV, and the affected area was spread across 1309.39 thousand hectares. The AOT40 exposure metric reached an average value of 11.490 ppbV, with a range of 0.000–31.665 ppbV. The highest exposure level was 17.503–31.653 ppbV, covering an area of 747.01 thousand hectares. The total CPL of the three rice crops over the LMD was 9593.52 tonnes (accounting for 0.039% of the total value of rice production in the region), with a total corresponding EPL of 62.405 billion VND (equivalent to 2761.01 thousand USD). The results are considered a baseline study to serve as a basis for extensive assessments for the following years and support for the environmental managers to propose control measures of O3 precursor emissions (NOx and VOCs) from man-made sectors as well as build protective solutions in rice farming in LMD shortly.

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.

Formation mechanism, precursor sensitivity and control strategies of summertime ozone on the Fenwei Plain, China

As one of the most polluted regions in China, the Fenwei Plain has suffered severe summertime ozone (O3) pollution in recent years. However, related studies in this region are still scarce. In this study, a comprehensive observation campaign was conducted in a typical city on the Fenwei Plain. An observation-based model (OBM) was used to investigate the summer O3 formation mechanism, precursor sensitivity and control strategies during O3-polluted and clean periods. Our results showed that O3 pollution was accompanied by increased O3 precursor concentrations (∼15% higher) and unfavorable meteorological conditions. In situ O3 production played a dominant role in the daytime O3 concentration increment in both polluted (+6.0 ppbv/h) and clean (+3.5 ppbv/h) periods. HO2 + NO (65.9%–66.7%) was the most dominant pathway of daytime O3 formation, and OH + NO2 (41.3%–63.1%) was the most dominant pathway of O3 destruction. Regional transport has a certain contribution to the occurrence of polluted days, as well as a diluting effect on clean days. Regional transport had a certain contribution effect on polluted days and a dilution effect on clean days. The southeastern regions were potential source regions of high O3, and the northwestern regions were potential source regions of low O3. When pollution occurred, the O3 formation control regimes transformed from a volatile organic compound (VOC)-limited regime to a transition regime, corresponding to an increase in precursor concentrations and stronger local O3 production. A 30% reduction in VOCs and a 20% reduction in NOx (VOCs/NOx ≈ 1.5) were determined to be the optimal control strategies to achieve the O3 control target (82 ppbv) in summer. VOC reductions should target reactive and O3-sensitive species (Oxygened VOCs, alkenes, aromatics) to effectively alleviate O3 pollution. This study could provide scientific support for local O3 pollution control on the Fenwei Plain.

Continuous Measurement and Molecular Compositions of Atmospheric Water‐Soluble Brown Carbon in the Nearshore Marine Boundary Layer of Northern China: Secondary Formation and Influencing Factors

AbstractUnderstanding the evolution of brown carbon (BrC) in the atmosphere is essential for investigating its climate effects. This study deployed a novel in‐situ BrC continuous observation system to firstly measure water‐soluble BrC absorption (AbsWS‐BrC) in an offshore island over the Bohai Sea in the winter of 2020. The AbsWS‐BrC abundance before the cold wave (BCW) was more than twice higher than that after the cold wave (ACW). This was mainly ascribed to the substantially suppressed formation of secondary WS‐BrC (WS‐BrCsec). Diurnal patterns of AbsWS‐BrC exhibited nighttime peaks, which derived from enhanced primary emissions and strong aqueous‐phase processes. Photochemical processes bleached daytime WS‐BrC during BCW, while daytime peaks of WS‐BrCsec emerged during ACW due to the weakened photobleaching effect. Statistical analysis indicated ambient temperature and relative humidity as well as total oxidized nitrogen (NO2 + NO3−) and reduced nitrogen (NH4+ + NH3) were the dominant factors promoting WS‐BrCsec. Moderate aerosol pH (>2.5) also facilitated the formation of WS‐BrCsec while no obvious dependences of WS‐BrCsec on gas‐particle partitioning of ammonia, O3, and sulfur precursors were found. At the molecular level, BrC chromophores with the identified compositions, carbon oxidation state, O/C, H/C, and absorption spectra were compared between the two periods. Characteristics of water‐soluble CHO‐ and CHON‐BrC were more of secondary origin during BCW, while primary emissions contributed significantly to BrC chromophores during ACW. This study highlights the advantage of high resolution BrC measurement in probing its dynamic evolution and influencing factors.

Seasonal variations of O3 formation mechanism and atmospheric photochemical reactivity during severe high O3 pollution episodes in the Pearl River Delta region

In this study, the seasonal differences of O3 formation and photochemical reactivity were investigated during the high O3 episodes observed in autumn of 2014 and winter of 2017 at a downwind rural site of Pearl River Delta region (Heshan site). The mixing ratios of O3 and NO2 were highest in the Period I of autumn, followed by the Period II of autumn and the winter period. Though the total concentrations of VOCs were comparable in these periods, alkenes made greater fraction of VOCs during Period I of autumn, while those of OVOCs and aromatics were higher in winter period, resulting in the largest contributions of alkenes (ROH(alkenes)) and OVOCs (ROVOCs) to the photochemical reactivity in autumn and winter, respectively. The ozonolysis of alkenes (especially for 1-pentene and isoprene) dominated HOx production during Period I of autumn, while in winter period, photolysis of OVOCs increased before noon, and made the greatest contribution to HOx production in late afternoon. As for the HOx destruction, reaction of OH + NO2 dominated in both seasons, with higher rates in Period I of autumn because of higher levels of radical and NO2. Furthermore, the variations in O3 precursors and radical budget resulted in different O3 formation and destruction rates, with the highest contribution from RO2 and NO to O3 formation, as well as photolysis and ozonolysis of alkenes for O3 destruction in Period I of autumn. The net O3 production from photochemistry and contributions of physical processes indicated that local photochemistry dominated the O3 accumulation at noon and in the early afternoon, while dilution in O3 levels caused by physical process increased before noon and in the late afternoon. O3 formation sensitivity could be changed during the photochemical consumption of precursors, which was more NOx-limited in the late afternoon. Overall, our findings highlighted that control measures of photochemical pollution should consider the seasonal variations in the abundance of O3 and its precursors, and O3 formation sensitivity regime.

Identify the key emission sources for mitigating ozone pollution: A case study of urban area in the Yangtze River Delta region, China

Ozone (O3) has become the most critical air pollutant in the Yangtze River Delta (YRD) region of China. Research on the O3 formation mechanism and its precursor sources (including nitrogen oxides (NOX) and volatile organic compounds (VOCs)) could provide a theoretical basis for mitigating O3 pollution in this region. In this study, simultaneous field experiments were conducted for air pollutants in a typical urban area (Suzhou) in the YRD region in 2022. The capacity of in-situ O3 formation, O3-NOX-VOCs sensitivities and sources of O3 precursors were analyzed. The results showed that in-situ formation contributed 20.8 % of the O3 concentration in the warm season (April to October) of the Suzhou urban area. Compared with the warm season average, the concentrations of various O3 precursors increased on pollution days. The O3-NOX-VOCs sensitivity was the VOCs-limited regime based on the average concentrations during the warm season. O3 formation was most sensitive to anthropogenic VOCs, of which oxygenated VOCs, alkenes and aromatics were the key species. There was a VOCs-limited regime in spring and autumn, while a transitional regime in summer due to the changes in NOX concentrations. This study considered NOX emission from VOCs sources and calculated the contribution of various sources to O3 formation. The results of VOCs source apportionment showed that diesel engine exhaust and fossil fuel combustion had a dominant proportion, but O3 formation presented significant negative sensitivities to the above two sources because of their high NOX emissions. There were significant sensitivities of O3 formation to gasoline vehicle exhaust and VOCs evaporative emissions (gasoline evaporation and solvent usage). The contribution of VOCs evaporative emissions during the O3 pollution episode was significantly higher than the average; therefore, controlling VOCs evaporative emissions during the O3 pollution episode is critical. These results provide feasible strategies to mitigate O3 pollution.

Contribution of atmospheric circulations changes to the variations of summertime lower tropospheric ozone over East Asia during recent decades

The formation of O3 pollution not only depends on the emission of the O3 precursors, but also is closely related to the atmospheric circulation. However, to what extent atmospheric circulation changes contribute to the variations of O3 concentration has not been well understood over East Asia. Here, the O3 concentration data from the ERA5 Reanalysis are employed to investigate the contribution of the atmospheric circulation to the summertime lower tropospheric O3 changes in East Asian continent (EC) during 1979–2021. Results show that the summertime lower tropospheric O3 displays the same-sign variations in the whole EC during 1979–2021. The Silk Road-like atmospheric teleconnection is identified as a key circulation factor to drive the variations of summer O3 concentration in EC. The deep anomalous anticyclone over EC not only strengthens the descending motion and increases the sunlight and air temperature in the lower troposphere, resulting in the acceleration of formation of O3, but also transports more O3 from northern East Asia to lower latitudes of EC, leading to more increasing of the O3 concentration in central and eastern China. Further analysis indicates that the Silk Road-like atmospheric wave train is associated with the North Atlantic sea surface temperature (SST) variability that accounts for about 43% of total variance of O3 concentration in EC. Sensitivity experiments run with ECHAM5 model confirm the impact of the North Atlantic SST anomalies on this atmospheric wave train. Hence, our finding provides an insight of the cause of the lower tropospheric O3 variations in EC.