Ozone Precursor Emissions Research Articles

Long-term changes in northern mid-latitude tropospheric ozone concentrations: Synthesis of two recent analyses

The HTAP (Hemispheric Transport of Air Pollution) and TOAR (Tropospheric Ozone Assessment Report) programs synthesized historical ozone measurements and compared them with recent measurements to quantify the long-term increase of tropospheric ozone concentrations that occurred at northern mid-latitudes in the 20th century due to the increase and subsequent stabilization of anthropogenic ozone precursor emissions. The two studies disagree regarding the magnitude of the increase; the HTAP study found an approximate doubling of baseline ozone concentrations, while the TOAR study suggested a change of about half that magnitude in the well-mixed planetary boundary layer. Here we explore the reasons for this difference, and reconcile the results. The two efforts agree regarding measurements of historical ozone concentrations, but disagree on the comparison of the historical to the modern data. HTAP analyzed seasonal mean historical and modern data from the same or closely equivalent, baseline sites. TOAR selected pre-1975 measurement data sets based upon four data selection criteria; averages of these selected data sets from all seasons, site locations and site environments were compared with annual means of modern data collected at rural European surface sites. The TOAR comparison approach introduced several biases that led to underestimates of the overall change of baseline ozone. We conclude that northern mid-latitude tropospheric baseline ozone concentrations, which are relevant for radiative forcing, increased by a factor of 2.1 ± 0.2 over the 1950–2000 period.

Ozone production and precursor emission from wildfires in Africa

Tropospheric ozone (O3) negatively impacts human health and is also a greenhouse gas.

Extending Ozone‐Precursor Relationships in China From Peak Concentration to Peak Time

AbstractHigh ozone concentrations have become the major summertime air quality problem in China. Extensive in situ observations are deployed for developing strategies to effectively control the emissions of ozone precursors, that is, nitrogen oxides (NOX = NO + NO2) and volatile organic compounds (VOCs). The modeling analysis of in situ observations often makes uses of the dependence of ozone peak concentration on NOX and VOC emissions, because ozone observations are among the most widely available air quality measurements. To extract more information from regulatory ozone observations, we extend the ozone‐precursor relationship to ozone peak time in this study. We find that the sensitivities of ozone peak time and concentration are complementary for regions with large anthropogenic emissions such as China. The ozone peak time is sensitive to both VOC and NOX emissions, and the sensitivity is nearly linear in the transition regime of ozone production compared to the changing ozone peak concentration sensitivity in this regime, making the diagnostics of ozone peak time particularly valuable. The extended ozone‐precursor relationships can be readily applied to understand the effects on ozone by emission changes of NOX and VOC and to assess potential biases of NOX and VOC emission inventories. These observation constraints based on regulatory ozone observations can complement the other measurement and modeling analysis methods nicely. Furthermore, we suggest that the ozone peak time sensitivity we discussed here to be used as a model evaluation measure before the empirical kinetic modeling approach (EKMA) diagram is applied to understand the effectiveness of emission control on ozone concentrations.

Trends in global tropospheric hydroxyl radical and methane lifetime since 1850 from AerChemMIP

Abstract. We analyse historical (1850–2014) atmospheric hydroxyl (OH) and methane lifetime data from Coupled Model Intercomparison Project Phase 6 (CMIP6)/Aerosols and Chemistry Model Intercomparison Project (AerChemMIP) simulations. Tropospheric OH changed little from 1850 up to around 1980, then increased by around 9 % up to 2014, with an associated reduction in methane lifetime. The model-derived OH trends from 1980 to 2005 are broadly consistent with trends estimated by several studies that infer OH from inversions of methyl chloroform and associated measurements; most inversion studies indicate decreases in OH since 2005. However, the model results fall within observational uncertainty ranges. The upward trend in modelled OH since 1980 was mainly driven by changes in anthropogenic near-term climate forcer emissions (increases in anthropogenic nitrogen oxides and decreases in CO). Increases in halocarbon emissions since 1950 have made a small contribution to the increase in OH, whilst increases in aerosol-related emissions have slightly reduced OH. Halocarbon emissions have dramatically reduced the stratospheric methane lifetime by about 15 %–40 %; most previous studies assumed a fixed stratospheric lifetime. Whilst the main driver of atmospheric methane increases since 1850 is emissions of methane itself, increased ozone precursor emissions have significantly modulated (in general reduced) methane trends. Halocarbon and aerosol emissions are found to have relatively small contributions to methane trends. These experiments do not isolate the effects of climate change on OH and methane evolution; however, we calculate residual terms that are due to the combined effects of climate change and non-linear interactions between drivers. These residual terms indicate that non-linear interactions are important and differ between the two methodologies we use for quantifying OH and methane drivers. All these factors need to be considered in order to fully explain OH and methane trends since 1850; these factors will also be important for future trends.

Role of export industries on ozone pollution and its precursors in China

This study seeks to estimate how global supply chain relocates emissions of tropospheric ozone precursors and its impacts in shaping ozone formation. Here we show that goods produced in China for foreign markets lead to an increase of domestic non-methane volatile organic compounds (NMVOCs) emissions by 3.5 million tons in 2013; about 13% of the national total or, equivalent to half of emissions from European Union. Production for export increases concentration of NMVOCs (including some carcinogenic species) and peak ozone levels by 20–30% and 6–15% respectively, in the coastal areas. It contributes to an estimated 16,889 (3,839–30,663, 95% CI) premature deaths annually combining the effects of NMVOCs and ozone, but could be reduced by nearly 40% by closing the technology gap between China and EU. Export demand also alters the emission ratios between NMVOCs and nitrogen oxides and hence the ozone chemistry in the east and south coast.

Trends in tropospheric ozone concentrations and forest impact metrics in Europe over the time period 2000\u20132014

In Europe, tropospheric ozone pollution appears as a major air quality issue, and ozone concentrations remain potentially harmful to vegetation. In this study we compared the trends of two ozone metrics widely used for forests protection in Europe, the AOT40 (Accumulated Ozone over Threshold of 40 ppb) which only depends on surface air ozone concentrations, and the Phytotoxic Ozone Dose which is the accumulated ozone uptake through stomata over the growing season, and above a threshold Y of uptake (PODY). By using a chemistry transport model, we found that European-averaged ground-level ozone concentrations (− 2%) and AOT40 metric (− 26.5%) significantly declined from 2000 to 2014, due to successful control strategies to reduce the emission of ozone precursors in Europe since the early 1990s. In contrast, the stomatal ozone uptake by forests increased from 17.5 to 26.6 mmol O3 m−2 despite the reduction in ozone concentrations, leading to an increase of potential ozone damage on plants in Europe. In a climate change context, a biologically-sound stomatal flux-based standard (PODY) as new European legislative standard is needed.

Lower air pollution during COVID-19 lock-down: improving models and methods estimating ozone impacts on crops.

We suggest that the unprecedented and unintended decrease of emissions of air pollutants during the COVID-19 lock-down in 2020 could lead to declining seasonal ozone concentrations and positive impacts on crop yields. An initial assessment of the potential effects of COVID-19 emission reductions was made using a set of six scenarios that variously assumed annual European and global emission reductions of 30% and 50% for the energy, industry, road transport and international shipping sectors, and 80% for the aviation sector. The greatest ozone reductions during the growing season reached up to 12 ppb over crop growing regions in Asia and up to 6 ppb in North America and Europe for the 50% global reduction scenario. In Europe, ozone responses are more sensitive to emission declines in other continents, international shipping and aviation than to emissions changes within Europe. We demonstrate that for wheat the overall magnitude of ozone precursor emission changes could lead to yield improvements between 2% and 8%. The expected magnitude of ozone precursor emission reductions during the Northern Hemisphere growing season in 2020 presents an opportunity to test and improve crop models and experimentally based exposure response relationships of ozone impacts on crops, under real-world conditions.This article is part of a discussion meeting issue ‘Air quality, past present and future’.

Emissions of nitrogen oxides and volatile organic compounds from liquefied petroleum gas-fueled taxis under idle and cruising modes

Liquefied petroleum gas (LPG) as an alternative fuel is increasingly used in mainland China, few reports are however available about emissions from LPG-fueled vehicles. In this study, 26 LPG-fueled taxis in Guangzhou, south China were tested using a chassis dynamometer to obtain their emission factors of nitrogen oxides (NOx) and volatile organic compounds (VOCs) under idle and cruising (10–60 km h−1) modes. The emission factors of NOx on average increased with speed from 4.13 g kg-fuel−1 at idling to 71.1 g kg-fuel−1 at 60 km h−1 at a slope of 10.6 g kg-fuel−1 per 10 km h−1 increase in speed. Alkanes were the most abundant (71.9%) among the VOCs in the exhaust, followed by alkenes (25.2%), ethyne (2.7%), and aromatic species (0.2%). Emission factors of VOCs at idling averaged 8.24 g kg-fuel−1, higher than that of 6.23–7.36 g kg-fuel−1 when cruising at 10–60 km h−1, but their ozone formation potentials (OFPs) were lower at idling (15.8 g kg-fuel−1) than under cruising (19.1–23.8 g kg-fuel−1) largely due to higher emission of more reactive alkenes under cruising mode. Emissions of both NOx and VOCs increased significantly with mileages. Measured emission factors of NOx and reactive VOCs in this study suggested that replacing the gasoline-powered taxis with the LPG-fueled taxis with LPG-gasoline bi-fuel engines and no efficient after-treatment devices would not benefit in reducing the emissions of ozone precursors, and strengthening the emission control for LPG vehicles with dedicated LPG engines and after-treatment converters, as did in Hong Kong, could further benefit in reducing the emission of photochemically active species when using LPG as alternative fuels.

Impact of U.S. Oil and Natural Gas Emission Increases on Surface Ozone Is Most Pronounced in the Central United States.

Observations of volatile organic compounds (VOCs) from a surface sampling network and simulation results from the EMAC (ECHAM5/MESSy for Atmospheric Chemistry) model were analyzed to assess the impact of increased emissions of VOCs and nitrogen oxides from U.S. oil and natural gas (O&NG) sources on air quality. In the first step, the VOC observations were used to optimize the magnitude and distribution of atmospheric ethane and higher-alkane VOC emissions in the model inventory for the base year 2009. Observation-based increases of the emissions of VOCs and NOx stemming from U.S. oil and natural gas (O&NG) sources during 2009–2014 were then added to the model, and a set of sensitivity runs was conducted for assessing the influence of the increased emissions on summer surface ozone levels. For the year 2014, the added O&NG emissions are predicted to affect surface ozone across a large geographical scale in the United States. These emissions are responsible for an increased number of days when the averaged 8-h ozone values exceed 70 ppb, with the highest sensitivity being in the central and midwestern United States, where most of the O&NG growth has occurred. These findings demonstrate that O&NG emissions significantly affect the air quality across most of the United States, can regionally offset reductions of ozone precursor emissions made in other sectors, and can have a determining influence on a region’s ability to meet National Ambient Air Quality Standard (NAAQS) obligations for ozone.

Vegetation feedbacks during drought exacerbate ozone air pollution extremes in Europe

Reducing surface ozone to meet the European Union’s target for human health has proven challenging despite stringent controls on ozone precursor emissions over recent decades. The most extreme ozone pollution episodes are linked to heatwaves and droughts, which are increasing in frequency and intensity over Europe, with severe impacts on natural and human systems. Here, we use observations and Earth system model simulations for the period 1960–2018 to show that ecosystem–atmosphere interactions, especially reduced ozone removal by water-stressed vegetation, exacerbate ozone air pollution over Europe. These vegetation feedbacks worsen peak ozone episodes during European mega-droughts, such as the 2003 event, offsetting much of the air quality improvements gained from regional emissions controls. As the frequency of hot and dry summers is expected to increase over the coming decades, this climate penalty could be severe and therefore needs to be considered when designing clean air policy in the European Union. Despite strict controls on precursor emissions, ozone air pollution has not decreased over Europe in recent decades. This is largely attributed to water-stressed vegetation; during heatwaves and drought, plants are less effective at ozone removal via stomata, worsening peak ozone pollution episodes.

Global sensitivity analysis of chemistry–climate model budgets of tropospheric ozone and OH: exploring model diversity

Abstract. Projections of future atmospheric composition change and its impacts on air quality and climate depend heavily on chemistry–climate models that allow us to investigate the effects of changing emissions and meteorology. These models are imperfect as they rely on our understanding of the chemical, physical and dynamical processes governing atmospheric composition, on the approximations needed to represent these numerically, and on the limitations of the observations required to constrain them. Model intercomparison studies show substantial diversity in results that reflect underlying uncertainties, but little progress has been made in explaining the causes of this or in identifying the weaknesses in process understanding or representation that could lead to improved models and to better scientific understanding. Global sensitivity analysis provides a valuable method of identifying and quantifying the main causes of diversity in current models. For the first time, we apply Gaussian process emulation with three independent global chemistry-transport models to quantify the sensitivity of ozone and hydroxyl radicals (OH) to important climate-relevant variables, poorly characterised processes and uncertain emissions. We show a clear sensitivity of tropospheric ozone to atmospheric humidity and precursor emissions which is similar for the models, but find large differences between models for methane lifetime, highlighting substantial differences in the sensitivity of OH to primary and secondary production. This approach allows us to identify key areas where model improvements are required while providing valuable new insight into the processes driving tropospheric composition change.

Sensitivity of Meteorological Skill to Selection of WRF‐Chem Physical Parameterizations and Impact on Ozone Prediction During the Lake Michigan Ozone Study (LMOS)

AbstractOzone concentrations in excess of health‐based standards occur along the coastline of Lake Michigan. A complex pattern of ozone precursor emissions interfaces with a complex meteorological environment, presenting a challenge for air quality management and simulation. Precursors are transported into a shallow, stable boundary layer over the lake. This is followed by ozone formation and transport back onshore through a combination of synoptic and lake breeze winds. In this study, we use measurements during the Lake Michigan Ozone Study 2017 (LMOS) to quantitatively evaluate the Weather Research and Forecasting with Chemistry (WRF‐Chem) model at 4 km horizontal resolution for key features of high ozone episodes over Southern Lake Michigan, with a focus on meteorological performance. WRF‐Chem showed good performance and successful reproduction of meteorological fields and clouds. Lake breeze model skill was inconsistent, with both good and poor performance depending on site and day. The combination of Noah land surface model and High‐Resolution Rapid Refresh meteorology gave the best performance with the mean bias of −0.5 °C for temperature, −0.6 °C for dewpoint temperature, and −0.3 m/s for wind speed along the western coast of Lake Michigan during the daytime. For ozone, WRF‐Chem was biased low (−4.4 ppb mean bias for daytime ozone) and underestimated hourly peak ozone. In some cases, ozone bias can be attributed to transport and lake breeze errors. Average ozone concentration showed minor (<2 ppb) sensitivity to changes to meteorology initial and boundary conditions or the land surface model.

Ozone-related asthma emergency department visits in the US in a warming climate

Ozone exposure is associated with higher risk of asthma-related emergency department visits. The meteorological conditions that govern ozone concentration are projected to be more favorable to ozone formation over much of the United States due to continued climate change, even as emissions of anthropogenic ozone precursors are expected to decrease by 2050. Our goal is to quantify the health benefits of a climate change mitigation scenario versus a “business-as-usual” scenario, defined by the United Nations Intergovernmental Panel on Climate Change Representative Concentration Pathways (RCPs) 4.5 and 8.5, respectively, using the health impact analytical program Benefits Mapping and Analysis Program – Community Edition (BenMAP – CE) to project the number of asthma ED visits in 2045–2055. We project an annual average of 3100 averted ozone-related asthma ED visits during the 2045–2055 period under RCP4.5 versus RCP8.5, with all other factors held constant, which translates to USD $1.7 million in averted costs annually. We identify counties with tens to hundreds of avoided ozone-related asthma ED visits under RCP4.5 versus RCP8.5. Overall, we project a heterogeneous distribution of ozone-related asthma ED visits at different spatial resolutions, specifically national, regional, and county levels, and a substantial net health and economic benefit of climate change mitigation.

Mitigation of ozone damage to the world’s land ecosystems by source sector

Surface ozone damages photosynthesis and reduces the ability of land ecosystems to assimilate carbon from the atmosphere thereby further increasing global warming1,2. Ozone is not emitted directly but formed in the atmosphere during complex chemical reactions of precursors, carbon monoxide, methane, non-methane volatile organic compounds and nitrogen oxides, in sunlight. These ozone precursors are emitted from a wide range of anthropogenic activities. Reductions in ozone precursor emissions are needed to mitigate ozone vegetation damage but it is unclear which are the most effective source sectors to target. Here, we apply a global Earth system model to compare the benefits to gross primary productivity of stringent 50% emission reductions in the seven largest anthropogenic ozone source sectors. Deep cuts in air pollutant emissions from road transportation and the energy sector are the most effective mitigation measures for ozone-induced gross primary productivity losses in Eastern China, Eastern United States, Europe and globally. Our results suggest that mitigation of ozone vegetation damage is a unique opportunity to contribute to negative carbon emissions, offering a natural climate solution that links fossil fuel emission abatement, air quality and climate. However, achieving these benefits requires ambitious mitigation pathways that tackle multiple source sectors. Ozone forms in the atmosphere when other anthropogenically emitted gases react with sunlight and negatively impacts terrestrial gross primary productivity (GPP). Reducing emissions of ozone precursors by 50%, particularly in the road transportation and energy sectors, could increase GPP by 750 TgC yr–1.

Multi-decadal surface ozone trends at globally distributed remote locations

Extracting globally representative trend information from lower tropospheric ozone observations is extremely difficult due to the highly variable distribution and interannual variability of ozone, and the ongoing shift of ozone precursor emissions from high latitudes to low latitudes. Here we report surface ozone trends at 27 globally distributed remote locations (20 in the Northern Hemisphere, 7 in the Southern Hemisphere), focusing on continuous time series that extend from the present back to at least 1995. While these sites are only representative of less than 25% of the global surface area, this analysis provides a range of regional long-term ozone trends for the evaluation of global chemistry-climate models. Trends are based on monthly mean ozone anomalies, and all sites have at least 20 years of data, which improves the likelihood that a robust trend value is due to changes in ozone precursor emissions and/or forced climate change rather than naturally occurring climate variability. Since 1995, the Northern Hemisphere sites are nearly evenly split between positive and negative ozone trends, while 5 of 7 Southern Hemisphere sites have positive trends. Positive trends are in the range of 0.5–2 ppbv decade–1, with ozone increasing at Mauna Loa by roughly 50% since the late 1950s. Two high elevation Alpine sites, discussed by previous assessments, exhibit decreasing ozone trends in contrast to the positive trend observed by IAGOS commercial aircraft in the European lower free-troposphere. The Alpine sites frequently sample polluted European boundary layer air, especially in summer, and can only be representative of lower free tropospheric ozone if the data are carefully filtered to avoid boundary layer air. The highly variable ozone trends at these 27 surface sites are not necessarily indicative of free tropospheric trends, which have been overwhelmingly positive since the mid-1990s, as shown by recent studies of ozonesonde and aircraft observations.

The Importance of Fundamental Science for Society: The Success Story of Ozone Research

AbstractThe successful story of ozone research from the discovery of this gas in the laboratory in 1839 to the protection of the stratospheric ozone layer by the Montreal Protocol in 1987 highlights the role and importance of fundamental research. None of the scientists who discovered the chemical nature and properties of ozone, and established its presence in the atmosphere, suspected that humans would be able to destroy a protective stratospheric layer that is essential for life on Earth. None of them had anticipated either that the emissions of pollutants associated with industrial activity and road transportation in urban areas would generate summertime ozone smog events with detrimental health effects and premature mortality. Scientific research has provided the knowledge needed to convince governments to take effective legislation to ban the industrial production of stratospheric ozone depleting agents and reduce the emissions of ozone precursors in the troposphere. This perspective paper calls for enhanced support of a strong fundamental research activity that rewards imagination and protects the scientific community from tight administrative and financial constraints. It highlights the need for scientists to keep a free and independent mind that leads to progress and innovation.

Elucidating emissions control strategies for ozone to protect human health and public welfare within the continental United States

Ground-level ozone, which forms photochemically in the atmosphere from precursor emissions of oxides of nitrogen (NOx) and volatile organic compounds, is a criteria pollutant that harms human health and public welfare. For a representative summer episode, premature mortality and potential productivity losses (PPLs) of selected crops and trees attributable to ozone exposure have been quantified using ozone fields from the Community Multiscale Air Quality (CMAQ) model. We applied exposure-response models for the increased risk of premature mortality due to long-term exposure to ozone over a theoretical minimum risk exposure level (TMREL) and for the reduced accumulation of vegetative biomass for four crop species and eleven tree species using the W126 metric designed to capture impacts on plants. To elucidate which emissions contributed to these disbenefits, we applied adjoint-based sensitivity analysis, which efficiently estimates sensitivities of concentration-based metrics with respect to numerous emissions parameters simultaneously. The adjoint of CMAQ was applied to the continental US to calculate the influence of spatially-resolved ozone precursor emissions on the annual average, domain-wide daily maximum 8 h average over the TMREL (elevated MDA8), premature mortality attributable to exposure to ozone above the TMREL, and PPLs. These quantities provide the impact in terms of the percent reduction in precursor emissions. Additionally, locations where similar percent reductions in ozone precursor emissions would impact one or more endpoints greater than average have been identified. NOx emissions were found to contribute most to the three metrics. The distinct spatial patterns of emissions influences on public welfare disbenefits as compared to the elevated MDA8 and premature mortality suggest that the current regulatory averaging time motivates different emissions control strategies than those that could most directly protect public welfare.

Identification and Quantification of Uncertainty Components in Gaseous and Particle Emission Measurements of a Moped

The recent Euro 4 and 5 environmental steps for L-category vehicles (e.g., mopeds, motorcycles) were mainly designed to reduce the emissions of particulate matter and ozone precursors, such as nitrogen oxides and hydrocarbons. However, the corresponding engine, combustion, and aftertreatment improvements will not necessarily reduce the solid particle number (SPN) emissions, suggesting that a SPN regulation may be necessary in the future. At the same time, there are concerns whether the current SPN regulations of passenger cars can be transferred to L-category vehicles. In this study we quantified the errors and uncertainties in emission measurements, focusing on SPN. We summarized the sources of uncertainty related to emission measurements and experimentally quantified the contribution of each uncertainty component to the final results. For this reason, gas analyzers and SPN instruments with lower cut-off sizes of 4 nm, 10 nm, and 23 nm were sampling both from the tailpipe, and from the dilution tunnel having the transfer tube in closed or open configuration (i.e., open at the tailpipe side). The results showed that extracting from the tailpipe 23–28% of the mean total exhaust flow (bleed off) resulted in a 24–31% (for CO2) and 19–73% (for SPN) underestimation of the emissions measured at the dilution tunnel. Erroneous determination of the exhaust flow rate, especially at cold start, resulted in 2% (for CO2) and 69–149% (for SPN) underestimation of the tailpipe emissions. Additionally, for SPN, particle losses in the transfer tube with the closed configuration decreased the SPN concentrations around 30%, mainly due to agglomeration at cold start. The main conclusion of this study is that the open configuration (or mixing tee) without any instruments measuring from the tailpipe is associated with better accuracy for mopeds, especially related to SPN measurements. In addition, we demonstrated that for this moped the particle emissions below 23 nm, the lower size currently prescribed in the passenger cars regulation, were as high as those above 23 nm; thus, a lower cut-off size is more appropriate.

Quantitative impacts of meteorology and precursor emission changes on the long-term trend of ambient ozone over the Pearl River Delta, China, and implications for ozone control strategy

Abstract. China is experiencing increasingly serious ambient ozone pollution, including the economically developed Pearl River Delta (PRD) region. However, the underlying reasons for the ozone increase remain largely unclear, leading to perplexity regarding formulating effective ozone control strategies. In this study, we quantitatively examine the impacts of meteorology and precursor emissions from within and outside of the PRD on the evolution of ozone during the past decade by developing a statistical analysis framework combining meteorological adjustment and source apportionment. We found that meteorological conditions mitigated ozone increase, and that their variation can account for a maximum of 15 % of the annual ozone concentration in the PRD. Precursor emissions from outside the PRD (“nonlocal”) have the largest contribution to ambient ozone in the region and show a consistently increasing trend, whereas emissions from within the PRD (“local”) show a significant spatial heterogeneity and play a more important role during ozone episodes over the southwest of the region. Under general conditions, the impact on the northeastern PRD is positive but decreasing, and in the southwest it is negative but increasing. During ozone episodes, the impact on the northeastern PRD is negative and decreasing, whereas in the southwestern PRD it is positive but decreasing. The central and western PRD are the only areas with an increasing local ozone contribution. The spatial heterogeneity in both the local ozone contribution and its trend under general conditions and during ozone episodes is well interpreted by a conceptual diagram that collectively takes ozone precursor emissions and their changing trends, ozone formation regimes, and the monsoonal and microscale synoptic conditions over different subregions of the PRD into consideration. In particular, we conclude that an inappropriate NOx∕VOC control ratio within the PRD over the past few years is most likely responsible for the ozone increase over southwest of this region, both under general conditions and during ozone episodes. By investigating the ozone evolution influenced by emission changes within and outside of the PRD during the past decade, this study highlights the importance of establishing a dichotomous ozone control strategy to tackle general conditions and pollution events separately. NOx emission control should be further strengthened to alleviate the peak ozone level during episodes. Detailed investigation is needed to retrieve appropriate NOx∕VOC ratios for different emission and meteorological conditions, so as to maximize the ozone reduction efficiency in the PRD.

Sensitivity of summer ozone to precursor emission change over Beijing during 2010–2015: A WRF-Chem modeling study

Beijing as the capital of China releases massive air pollutants and experiences the worsening summer O3 pollution recently. This study estimates Beijing ozone precursor emission, anthropogenic VOCs (AVOCs) being 325.3 kilotons in 2010, 231.8 kilotons in 2013 and 190.7 kilotons in 2015 and NOx being 211.3 kilotons in 2010, 238.3 kilotons in 2013 and 166.2 kilotons in 2015. Then, we conduct surface O3 simulation based on WRF-Chem through using different precursor emissions, to evaluate the influence of precursor control measures on Beijing O3. From 2010 to 2013, AVOCs reduction in Beijing would lead to O3 decrease in urban and suburban areas and O3 increase in some parts of northern rural areas; while from 2013 to 2015, AVOCs and NOx reductions would produce O3 increase in urban and northern suburban areas and O3 decrease in southern suburban and northern rural areas. Overall, the synergic reduction during 2010–2015 could effectively mitigate summer O3 pollution over Beijing, with daily maximum 1-h ozone (DAM1h O3) reduction exceeding 3 ppb. Finally, based on 2015 emission condition, 30% NOx and 30% VOCs emission reduction are further simulated to study O3-NOx-VOCs sensitivity over Beijing. The simulated DAM1h O3 reduction due to NOx- or VOCs-reduction shows that O3 is predominantly sensitive to VOCs in urban and northern suburban Beijing, but seems to be control more by the mixed chemistry in southern suburban and northern rural Beijing. However, NOx-sensitive condition is never found in rural Beijing. The distribution of simulated H2O2/HNO3 for the distinguished VOCs- and NOx-sensitive grids shows that 95th percentile for VOCs-sensitive distribution and 5th percentile for the NOx-sensitive distribution are 2.48 and 1.17 in all simulated days. According to the determined transition values, most Beijing is under VOCs-sensitive regime on the condition of 2015 precursor emission.