Ppbv Yr Research Articles

Impacts of global biogenic isoprene emissions on surface ozone during 2000–2019

Biogenic isoprene is an important precursor of tropospheric ozone (O3). Here, a coupled chemistry–vegetation model was used to quantify the contributions of isoprene emissions to surface O3 pollution on the global scale during 2000–2019. The biogenic isoprene emissions showed high values in mid–low latitudes and seasonal peaks in the summer hemispheres. They promote global surface O3 concentrations by 1.75 ppbv annually with regional hotspots of 4.39 ppbv (8.8%) in China and 5.36 ppbv (11.1%) in the U.S. in boreal summer. In the past two decades, isoprene emissions increased by 1.32 TgC yr−1 (0.67% yr−1) in the Northern Hemisphere but decreased by 0.71 TgC yr−1 (0.44% yr−1) in the Southern Hemisphere. Such changes of isoprene made opposite contributions to the surface O3 trend, with 0.26 ppbv yr−1 in eastern China but −0.32 ppbv yr−1 in the southeastern U.S. due to the changes in the background regime of chemical reactions. The impact of anthropogenic changes on the O3 trend is consistent with that of biogenic isoprene, but two to four times stronger in magnitude. This study revealed that the effective control of anthropogenic NOx emissions could mitigate regional O3 pollution even with the increased isoprene emissions under global warming.

Drivers and impacts of decreasing concentrations of atmospheric volatile organic compounds (VOCs) in Beijing during 2016–2020

China has implemented various policies and measures for controlling air pollutants. However, our knowledge of the long-term trends in ambient volatile organic compounds (VOCs) after the implementation of these action plans in China remains limited. To address this, we conducted a five-year analysis (2016–2020) of VOC compositions and concentrations in Beijing. The annual VOC concentration decreased from 44.0 ± 28.8 to 26.2 ± 16.4 ppbv, with alkanes being the most prevalent group. The annual average concentrations of alkenes, alkynes, and aromatics have experienced a significant decrease of over 50 %. Seasonal variations indicated higher VOC concentrations in winter and autumn, with more significant reductions observed in winter and autumn. The impact of meteorological conditions caused variations in VOC reductions during the Chinese Spring Festival. Satellite-based measurements of formaldehyde (HCHO) columns confirmed the reduction of VOC emissions during the Coronavirus (COVID-19) lockdown. The normalized annual average VOC concentration decreased by 2.9ppbv yr−1 from 2016 to 2020, and emission reduction contributed to 58.8 % of VOC reduction from 2016 to 2020 after meteorological normalization, indicating the effectiveness of implemented control measures. Based on receptor model, vehicle emissions and industrial sources were identified as the largest contributors to VOC concentrations. Vehicle emissions, liquefied petroleum gas/natural gas (LPG/NG) use, and coal combustion were major drivers of VOC reduction. Potential source region analysis revealed that air masses transported from northwestern and southern regions significantly contributed to VOC concentrations in Beijing. The range of source regions shrunk in both northwestern and southern regions with the reduction in VOC concentrations. The annual variations of ozone formation potential indicated a significant decrease in VOC reactivities through emission control. These results could provide insights into future emission control and coordinated efforts to improve PM2.5 and ozone levels in China.

Differences in MOPITT surface level CO retrievals and trends from Level 2 and Level 3 products in coastal grid boxes

Abstract. Users of MOPITT (Measurement of Pollution in the Troposphere) data are advised to discard retrievals performed over water from analyses. This is because MOPITT retrievals are more sensitive to near-surface CO when performed over land than water, meaning that they have a greater measurement component and are less tied to the a priori CO concentrations (which are taken from a model climatology) that are necessarily used in their retrieval. MOPITT Level 3 (L3) products are a 1∘ × 1∘ gridded average of finer-resolution (∼ 22 × 22 km) Level 2 (L2) retrievals. In the case of coastal L3 grid boxes, L2 retrievals performed over both land and water may be averaged together to create the L3 product, with L2 retrievals over land not contributing to the average at all in certain situations. This conflicts with data usage recommendations. The aim of this paper is to highlight the consequences that this has on surface level retrievals and their temporal trends in “as-downloaded” L3 data (L3O), by comparing them to those obtained if only the L2 retrievals performed over land are averaged to create the L3 product (L3L), for all identified coastal L3 MOPITT grid boxes. First, the difference between surface level retrievals in L3L and the corresponding L2 retrievals performed over water (L3W) is established for days when they are averaged together to create the L3O product for coastal grid boxes (yielding an L3O surface index of “mixed”, L3OM). Mean retrieved volume mixing ratios (VMRs) in L3L differ by over 10 ppbv from those in L3W, and temporal trends detected in L3L are between 0.28 and 0.43 ppbv yr−1 stronger than in L3W, on average. These L3L − L3W differences are clearly linked to retrieval sensitivity differences, with L3W being more heavily tied to the a priori CO profiles used in the retrieval, which are a model-derived monthly mean climatology that, by definition, has no trend year to year. VMRs in the resulting L3OM are significantly different to L3L for 45 % of all coastal grid boxes, corresponding to 75 % of grid boxes where the L3L − L3W difference is also significant. Just under half of the grid boxes that featured a significant L3L − L3W trend difference also see trends differing significantly between L3L and L3OM. Factors that determine whether L3OM and L3L differ significantly include the proportion of the surface covered by land/water and the magnitude of land–water contrast in retrieval sensitivity. Comparing the full L3O dataset to L3L, it is shown that if L3O is filtered so that only retrievals over land (L3OL) are analysed – as recommended – there is a huge loss of days with data for coastal grid boxes. This is because L2 retrievals over land are routinely discarded during the L3O creation process for these grid boxes. There is less data loss if L3OM retrievals are also retained, but the resulting L3O “land or mixed” (L3OLM) subset still has fewer data days than L3L for 61 % of coastal grid boxes. As shown, these additional days with data feature some influence from retrievals made over water, demonstrably affecting mean VMRs and their trends. Coastal L3 grid boxes contain 33 of the 100 largest coastal cities in the world, by population. Focusing on the L3 grid boxes containing these cities, it is shown that mean VMRs in L3OL and L3L differ significantly for 11 of the 27 grid boxes that can be compared (there are no L3OL data for 6 of the grid boxes studied), with 9 of the 18 grid boxes where temporal trend analysis can be performed in L3OL featuring a trend that is significantly different to that in L3L. These differences are a direct result of the data loss in L3OL – data that are available in L2 data (and are incorporated into the L3L product created for this study). The L3L − L3OLM mean VMR difference exceeds 10 (22) ppbv for 11 (3) of these 33 grid boxes, significant in 13 cases, with significant temporal trend differences in 5 cases. It is concluded that an L3 product based only on L2 retrievals over land – the L3L product analysed in this paper, available for public download – could be of benefit to MOPITT data users.

Trends in sulfur dioxide over the Indian subcontinent during 2003–2019

Sulfur dioxide (SO2) and its oxidation products profoundly impact the air quality and climate. In recent decades, contrasting SO2 trends have been observed over different regions of the globe due to urbanization, energy generation and control measures. In this study, we have investigated the SO2 trends over the rapidly developing Indian subcontinent using model reanalysis, satellite data, and emission inventories during 2003–2019 period. Copernicus Atmosphere Monitoring Service (CAMS) reanalysis shows rapid SO2 growth up to 0.4 ppbv yr−1 during 2003–2009, particularly significant over the Indo-Gangetic Plain (IGP) and eastern India. However, the growth becomes slower after 2010 and is followed by a stabilization or slight reduction. The CAMS results agree with the satellite-based observations, however, the model underestimates enhancements over eastern India. The analysis of inventory datasets also suggests slower growths in SO2 emissions and coal-fired electricity generation in recent years. Besides the changes in regional emissions, the enhancements in water vapor and OH radical coinciding with SO2 stabilization indicate strengthening of the sink processes. Model simulation (Modern-Era Retrospective analysis for Research and Applications version 2―MERRA-2) with constant emissions shows reduction in SO2 which confirms the stronger chemical losses. Overall, the SO2 trends over the Indian subcontinent are found to be a manifestation of the combined effects of the regional emission change and chemistry. Our findings highlight the need for studies to assess the impacts of changing SO2 trends in India on the regional and global climate.

Assessment of background ozone concentrations in China and implications for using region-specific volatile organic compounds emission abatement to mitigate air pollution

Mitigation of ambient ozone (O3) pollution is a great challenge because it depends heavily on the background O3 which has been poorly evaluated in many regions, including in China. By establishing the relationship between O3 and air temperature near the surface, the mean background O3 mixing ratios in the clean and polluted seasons were determined to be 35–40 and 50–55 ppbv in China during 2013–2019, respectively. Simulations using the chemical transport model (i.e., the Weather Research and Forecasting coupled with Chemistry model, WRF/Chem) suggested that biogenic volatile organic compounds (VOC) emissions were the primary contributor to the increase in the background O3 in the polluted season (BOP) compared to the background O3 in the clean season (BOC), ranging from 8 ppbv to 16 ppbv. More importantly, the BOP continuously increased at a rate of 0.6–8.0 ppbv yr−1 during 2013–2019, while the non-BOP stopped increasing after 2017. Consequently, an additional 2%–16% reduction in anthropogenic VOC emissions is required to reverse the current O3 back to that measured in the period from 2013 to 2017. The results of this study emphasize the importance of the relative contribution of the background O3 to the observed total O3 concentration in the design of anthropogenic precursor emission control strategies for the attainment of O3 standards.

Exploring the drivers of the increased ozone production in Beijing in summertime during 2005–2016

Abstract. In the past decade, average PM2.5 concentrations decreased rapidly under the strong pollution control measures in major cities in China; however, ozone (O3) pollution emerged as a significant problem. Here we examine a unique (for China) 12-year data set of ground-level O3 and precursor concentrations collected at an urban site in Beijing (PKUERS, campus of Peking University), where the maximum daily 8 h average (MDA8) O3 concentration and daytime Ox (O3+NO2) concentration in August increased by 2.3±1.2 ppbv (+3.3±1.8 %) yr−1 and 1.4±0.6 (+1.9±0.8 %) yr−1, respectively, from 2005 to 2016. In contrast, daytime concentrations of nitrogen oxides (NOx) and the OH reactivity of volatile organic compounds (VOCs) both decreased significantly. Over this same time, the decrease of particulate matter (and thus the aerosol optical depth) led to enhanced solar radiation and photolysis frequencies, with near-surface J(NO2) increasing at a rate of 3.6±0.8 % yr−1. We use an observation-based box model to analyze the combined effect of solar radiation and ozone precursor changes on ozone production rate, P(O3). The results indicate that the ratio of the rates of decrease of VOCs and NOx (about 1.1) is inefficient in reducing ozone production in Beijing. P(O3) increased during the decade due to more rapid atmospheric oxidation caused to a large extent by the decrease of particulate matter. This elevated ozone production was driven primarily by increased actinic flux due to PM2.5 decrease and to a lesser extent by reduced heterogeneous uptake of HO2. Therefore, the influence of PM2.5 on actinic flux and thus on the rate of oxidation of VOCs and NOx to ozone and to secondary aerosol (i.e., the major contributor to PM2.5) is important for determining the atmospheric effects of controlling the emissions of the common precursors of PM2.5 and ozone when attempting to control these two important air pollutants.

A measurement and model study on ozone characteristics in marine air at a remote island station and its interaction with urban ozone air quality in Shanghai, China

Abstract. To understand the characteristics and changes of baseline ozone (O3) in oceanic air in eastern China, a 6-year measurement of O3 concentration was conducted from 1 January 2012 to 15 September 2017 at a remote offshore station located on Sheshan Island (SSI) near the megacity of Shanghai. The observed monthly mean O3 concentrations at SSI ranged from 33.4 to 61.4 ppbv during the study period, which were about 80 % and 12 % higher, respectively, than those measured at downtown and rural sites in Shanghai. Compared to the remarkable O3 increases observed at urban and rural sites in Shanghai, observed O3 concentrations at SSI exhibited statistically insignificant increasing changes (1.12 ppbv yr−1, α>0.10) during the observation period, suggesting less impacts of anthropogenic emissions on O3 levels in oceanic air. In addition, an insignificant decreasing change (−0.72 ppbv yr−1, α>0.10) was detected in O3 concentrations at SSI in September and October when the influence of regional transport was minimum throughout the year, providing a good proxy to study the baseline oxidation capacity of the oceanic atmosphere. City plumes from Shanghai usually carried higher levels of NOx, resulting in decreased O3 concentrations at SSI during southwesterly and westerly winds. However, In MAM (March–May) and JJA (June–August), due to the enhanced production of oxygenated volatile organic compounds, O3 could be continuously produced during daytime in aged city plumes, resulting in elevated O3 concentrations transported to SSI. The impacts of the offshore O3 on O3 levels in Shanghai are quantified during an easterly wind dominant episode (1–30 September 2014) using the WRF-Chem model (Weather Research and Forecasting model coupled with Chemistry). Sensitivity results suggest that O3 in the oceanic air inflows can lead to 20 %–30 % increases in urban O3 concentrations, which should be crucially considered in dealing with urban O3 pollution in large coastal cities like Shanghai.

Quantifying the anthropogenic and meteorological influences on summertime surface ozone in China over 2012–2017

We applied the global 3-D chemical transport model GEOS-Chem to examine the anthropogenic and meteorological contributions in driving summertime (JJA) surface ozone (O3) trend in China during the Clean Air Action period 2012–2017. The model captures the observed spatial distribution of summertime O3 concentrations in China (R = 0.78) and reproduces the observed increasing trends in two most populated city clusters: North China Plain (NCP) and Yangtze River Delta (YRD). Trend of simulated maximum daily 8-h average (MDA8) O3 concentration is 0.58 ppbv yr−1 in NCP and 1.74 ppbv yr−1 in YRD in JJA 2012–2017. Sensitivity studies show that both changes in anthropogenic emissions and meteorology favored the MDA8 O3 increases in these two regions with respective contributions of 39% and 49% in NCP, and 13% and 84% in YRD. In NCP, the 49% meteorology impact includes a considerable contribution from natural emissions (19%). Changes in biogenic VOCs, soil NOx, and lightning NOx emissions are estimated to enhance MDA8 O3 in NCP with a rate of 0.14, 0.10, and 0.14 ppbv yr−1, respectively. In YRD, natural emissions made small contributions to the MDA8 O3 trend. Statistical analysis shows that higher temperatures and anomalous southerlies at 850 hPa in 2017 relative to 2012 are the two major meteorological drivers in NCP that favored the O3 increases, while weaker wind speed and lower relative humidity are those for YRD. We further examined the trend of fourth highest daily maximum 8-h average (4MDA8) O3 among a specific month that linked with extreme pollution episodes. Trends of simulated 4MDA8 O3 in NCP and YRD are 34–46% higher than those of MDA8 O3 and are found more meteorology-induced. Our results suggest an important role of meteorology in driving summertime O3 increases in China in recent years.

The trend of surface ozone in Beijing from 2013 to 2019: Indications of the persisting strong atmospheric oxidation capacity

We report a continuous record of surface ozone (O3) in urban Beijing, China, from 2013 to 2019. A linear fit to the 7-year record shows that the annual MDA8-O3 (the maximum daily average of 8-h O3 concentration) and annual average O3 increased by 2.30 and 1.91 ppbv yr−1 (p < 0.05), respectively. Both the MDA8-O3 level and the number of exceeding days are increased, demonstrating the surface O3 pollution in Beijing is increasingly serious. An overall decrease in annual surface NO2 was observed at a rate of −1.21 ppbv yr−1 (p < 0.01). The total oxidants (Ox, = NO2 + O3) had an upward trend during 2013–2019 at a rate of 0.70 ppbv h−1 (p = 0.168). The increasing O3 and Ox trends imply the atmospheric oxidation capacity is increasing in Beijing, even though the strict emission policies have been implemented. The periodical changes of surface O3 in different time scales are studied. We found that the increases in O3 are mainly at a high O3 level with a threshold of 30 ppbv. The relative diurnal variability of surface O3 is weakened, with a decrease in the diurnal amplitude variation. Both the extremely low and high 5% surface O3 are increased, indicates an overall uplift of surface O3. The weekday periodic trends showed an increment of weekend MDA8-O3 (2.2 ppbv on average) and companies with a decrement of weekend NO2 (1.5 ppbv on average). The weekend effect provides a chance to look insights into reducing O3 exceeding days during summertime and proposes the need for emission abatements of volatile organic compounds to the mitigation of ozone pollution in Beijing.

Impact of land–water sensitivity contrast on MOPITT retrievals and trends over a coastal city

Abstract. We compare MOPITT Version 7 (V7) Level 2 (L2) and Level 3 (L3) carbon monoxide (CO) products for the 1∘×1∘ L3 grid box containing the coastal city of Halifax, Canada (longitude −63.58∘, latitude 44.65∘), with a focus on the seasons DJF and JJA, and highlight a limitation in the L3 products that has significant consequences for the temporal trends in near-surface CO identified using those data. Because this grid box straddles the coastline, the MOPITT L3 products are created from the finer spatial resolution L2 products that are retrieved over both land and water, with a greater contribution from retrievals over water because more of the grid box lies over water than land. We create alternative L3 products for this grid box by separately averaging the bounded L2 retrievals over land (L3L) and water (L3W) and demonstrate that profile and total column CO (TCO) concentrations, retrieved at the same time, differ depending on whether the retrieval took place over land or water. These differences (ΔRET) are greatest in the lower troposphere (LT), where mean retrieved volume mixing ratios (VMRs) are greater in L3W than L3L, with maximum mean differences of 11.6 % (14.3 ppbv, p=0.001) at the surface level in JJA. Retrieved CO concentrations are more similar, on average, in the middle and upper troposphere (MT and UT), although large differences (in excess of 40 %) do infrequently occur. TCO is also greater in L3W than L3L in both seasons. By analysing L3L and L3W retrieval averaging kernels and simulations of these retrievals, we demonstrate that, in JJA, ΔRET is strongly influenced by differences in retrieval sensitivity over land and water, especially close to the surface where L3L has significantly greater information content than L3W. In DJF, land–water differences in retrieval sensitivity are much less pronounced and appear to have less of an impact on ΔRET, which analysis of wind directions suggests is more likely to reflect differences in true profile concentrations (i.e. real differences). The original L3 time series for the 1∘×1∘ grid box containing Halifax (L3O) corresponds much more closely to L3W than L3L, owing to the greater contribution from L2 retrievals over water than land. Thus, in JJA, variability in retrieved CO concentrations close to the surface in L3O is suppressed compared to L3L, and a declining trend detected using weighted least squares (WLS) regression analysis is significantly slower in L3O (strongest surface level trend identifiable is −1.35 (±0.35) ppbv yr−1) than L3L (−2.85 (±0.60) ppbv yr−1). This is because contributing L2 retrievals over water are closely tied to a priori CO concentrations used in the retrieval, owing to their lack of near-surface sensitivity in JJA, and these are based on monthly climatological CO profiles from a chemical transport model and therefore have no yearly change (surface level trend in L3W is −0.60 (±0.33) ppbv yr−1). Although our analysis focuses on DJF and JJA, we demonstrate that the findings also apply to MAM and SON. The results that we report here suggest that similar analyses be performed for other coastal cities before using MOPITT surface CO.

The long-term trend and production sensitivity change in the US ozone pollution from observations and model simulations

Abstract. We investigated the ozone pollution trend and its sensitivity to key precursors from 1990 to 2015 in the United States using long-term EPA Air Quality System (AQS) observations and mesoscale simulations. The modeling system, a coupled regional climate–air quality model (CWRF-CMAQ; Climate-Weather Research Forecast and the Community Multiscale Air Quality), captured well the summer surface ozone pollution during the past decades, having a mean slope of linear regression with AQS observations of ∼0.75. While the AQS network has limited spatial coverage and measures only a few key chemical species, CWRF-CMAQ provides comprehensive simulations to enable a more rigorous study of the change in ozone pollution and chemical sensitivity. Analysis of seasonal variations and diurnal cycle of ozone observations showed that peak ozone concentrations in the summer afternoon decreased ubiquitously across the United States, up to 0.5 ppbv yr−1 in major non-attainment areas such as Los Angeles, while concentrations at certain hours such as the early morning and late afternoon increased slightly. Consistent with the AQS observations, CMAQ simulated a similar decreasing trend of peak ozone concentrations in the afternoon, up to 0.4 ppbv yr−1, and increasing ozone trends in the early morning and late afternoon. A monotonically decreasing trend (up to 0.5 ppbv yr−1) in the odd oxygen (Ox=O3+NO2) concentrations are simulated by CMAQ at all daytime hours. This result suggests that the increased ozone in the early morning and late afternoon was likely caused by reduced NO–O3 titration, driven by continuous anthropogenic NOx emission reductions in the past decades. Furthermore, the CMAQ simulations revealed a shift in chemical regimes of ozone photochemical production. From 1990 to 2015, surface ozone production in some metropolitan areas, such as Baltimore, has transited from a VOC-sensitive environment (&gt;50 % probability) to a NOx-sensitive regime. Our results demonstrated that the long-term CWRF-CMAQ simulations can provide detailed information of the ozone chemistry evolution under a changing climate and may partially explain the US ozone pollution responses to regional and national regulations.

Decreased gaseous carbonyls in the North China plain from 2004 to 2017 and future control measures

Gaseous carbonyls are important precursors of ozone and secondary organic aerosols. To study the characteristics of small-molecule carbonyls (SMC), samples were collected with 2, 4-dinitrophenylhydrazine in Xianghe at the junction of the Beijing, Tianjin and Hebei regions from November 2017 to January 2018 and were subjected to high-performance liquid chromatography-ultraviolet analysis. The mean concentration of SMC was 4.5 ± 1.1 ppbv, and the observed compounds included acetone (1.9 ± 1.3 ppbv), acetaldehyde (1.3 ± 1.0 ppbv) and formaldehyde (1.2 ± 0.9 ppbv). Compared with the observations in the Beijing-Tianjin-Hebei region from 2004 to 2017, the concentration of SMC decreased and the trends were −1.13, −0.44 and −0.45 ppbv yr−1, respectively. Using volatile organic compounds as tracers, positive matrix factorization was used to analyze the sources of the SMC. The results showed that, in addition to secondary and long-lived species (84.8%), the main sources of SMC in Xianghe were vehicle emission (8.5%), solvent usage (3.7%) and coal and biomass combustion (3.0%). The significant decline in the contributions of vehicle emissions, coal and biomass combustion is the main reason for the decline in the SMC concentrations. Based on fine particulate matter concentrations, this study found that with the deterioration in air quality, the contribution of each source changed insignificantly. Although the concentrations of SMC dropped significantly, vehicular sources remained the most important sources in this region.

Measurement and model analyses of the ozone variation during 2006 to 2015 and its response to emission change in megacity Shanghai, China

Abstract. The fine particles (PM2.5) in China have decreased significantly in recent years as a result of the implementation of Chinese Clean Air Action Plan since 2013, while the O3 pollution is getting worse, especially in megacities such as Beijing and Shanghai. Better understanding of the elevated O3 pollution in Chinese megacities and its response to emission change is important for developing an effective emission control strategy in the future. In this study, we analyze the significant increasing trend of daily maximum O3 concentration from 2006 to 2015 in the megacity Shanghai with the variability of 0.8–1.3 ppbv yr−1. It could likely be attributed to the notable reduction in NOx concentrations with the decreasing rate of 1.86–2.15 ppbv yr−1 accompanied by the small change in VOCs during the same period by excluding the weak trends of meteorological impacts on local dispersion (wind speed), regional transport (wind direction), and O3 photolysis (solar radiation). It is further illustrated by using a state-of-the-art regional chemical and dynamical model (WRF-Chem) to explore the O3 variation response to the reduction in NOx emissions in Shanghai. The control experiment conducted for September of 2009 shows excellent performance for O3 and NOx simulations, including both the spatial distribution pattern and the day-by-day variation through comparison with six in situ measurements from the MIRAGE-Shanghai field campaign. Sensitivity experiments with 30 % reduction in NOx emissions from 2009 to 2015 in Shanghai estimated by Shanghai Environmental Monitoring Center shows that the calculated O3 concentrations exhibit obvious enhancement by 4–7 ppbv in urban zones with increasing variability of 0.96–1.06 ppbv yr−1, which is consistent with the observed O3 trend as a result of the strong VOC-limited condition for O3 production. The large reduction in NOx combined with less change in VOCs in the past 10 years promotes the O3 production in Shanghai to move towards an NOx-limited regime. Further analysis of the WRF-Chem experiments and O3 isopleth diagram suggests that the O3 production downtown is still under a VOC-limited regime after 2015 despite the remarkable NOx reduction, while it moves to the transition regime between NOx-limited and VOC-limited in sub-urban zones. Supposing the insignificant VOC variation persists, the O3 concentration downtown would keep increasing until 2020 with the further 20 % reduction in NOx emission after 2015 estimated by Shanghai Clean Air Action Plan. The O3 production in Shanghai will switch from a VOC-limited to an NOx-limited regime after 2020 except for downtown area, which is likely close to the transition regime. As a result the O3 concentration will decrease by 2–3 ppbv in sub-urban zones and by more than 4 ppbv in rural areas as a response to a 20 % reduction in NOx emission after 2020, whereas it is not sensitive to both NOx and VOC changes downtown. This result reveals that the control strategy of O3 pollution is a very complex process and needs to be carefully studied.

Intercomparison of O&amp;lt;sub&amp;gt;3&amp;lt;/sub&amp;gt; formation and radical chemistry in the past decade at a suburban site in Hong Kong

Abstract. Hong Kong, as one of the densely populated metropolises in East Asia, has been suffering from severe photochemical smog in the past decades, though the observed nitrogen oxides (NOx) and total volatile organic compounds (TVOCs) were significantly reduced. This study, based on the observation data in the autumns of 2007, 2013 and 2016, investigated the photochemical ozone (O3) formation and radical chemistry during the three sampling periods in Hong Kong with the aid of a photochemical box model incorporating the Master Chemical Mechanism (PBM–MCM). While the simulated locally produced O3 remained unchanged (p=0.73) from 2007 to 2013, the observed O3 increased (p &lt; 0.05) at a rate of 1.78 ppbv yr−1 driven by the rise in regionally transported O3 (1.77±0.04 ppbv yr−1). Both the observed and locally produced O3 decreased (p &lt; 0.05) from the VOC sampling days in 2013 to those in 2016 at a rate of -5.31±0.07 and -5.52±0.05 ppbv yr−1, respectively. However, a leveling-off (p=0.32) was simulated for the regionally transported O3 during 2013–2016. The mitigation of autumn O3 pollution in this region was further confirmed by the continuous monitoring data, which have never been reported. Benefiting from the air pollution control measures taken in Hong Kong, the local O3 production rate decreased remarkably (p &lt; 0.05) from 2007 to 2016, along with the lowering of the recycling rate of the hydroxyl radical (OH). Specifically, VOCs emitted from the source of liquefied petroleum gas (LPG) usage and gasoline evaporation decreased in this decade at a rate of -2.61±0.03 ppbv yr−1, leading to a reduction of the O3 production rate from 0.51±0.11 ppbv h−1 in 2007 to 0.10±0.02 ppbv h−1 in 2016. In addition, solvent usage made decreasing contributions to both VOCs (rate =-2.29±0.03 ppbv yr−1) and local O3 production rate (1.22±0.17 and 0.14±0.05 ppbv h−1 in 2007 and 2016, respectively) in the same period. All the rates reported here were for the VOC sampling days in the three sampling campaigns. It is noteworthy that meteorological changes also play important roles in the inter-annual variations in the observed O3 and the simulated O3 production rates. Evaluations with more data in longer periods are therefore recommended. The analyses on the decadal changes of the local and regional photochemistry in Hong Kong in this study may be a reference for combating China's nationwide O3 pollution in near future.

Ozone response to emission reductions in the southeastern United States

Abstract. Ozone (O3) formation in the southeastern US is studied in relation to nitrogen oxide (NOx) emissions using long-term (1990s–2015) surface measurements of the Southeastern Aerosol Research and Characterization (SEARCH) network, U.S. Environmental Protection Agency (EPA) O3 measurements, and EPA Clean Air Status and Trends Network (CASTNET) nitrate deposition data. Annual fourth-highest daily peak 8 h O3 mixing ratios at EPA monitoring sites in Georgia, Alabama, and Mississippi exhibit statistically significant (p &lt; 0.0001) linear correlations with annual NOx emissions in those states between 1996 and 2015. The annual fourth-highest daily peak 8 h O3 mixing ratios declined toward values of ∼ 45–50 ppbv and monthly O3 maxima decreased at rates averaging ∼ 1–1.5 ppbv yr−1. Mean annual total oxidized nitrogen (NOy) mixing ratios at SEARCH sites declined in proportion to NOx emission reductions. CASTNET data show declining wet and dry nitrate deposition since the late 1990s, with total (wet plus dry) nitrate deposition fluxes decreasing linearly in proportion to reductions of NOx emissions by ∼ 60 % in Alabama and Georgia. Annual nitrate deposition rates at Georgia and Alabama CASTNET sites correspond to 30 % of Georgia emission rates and 36 % of Alabama emission rates, respectively. The fraction of NOx emissions lost to deposition has not changed. SEARCH and CASTNET sites exhibit downward trends in mean annual nitric acid (HNO3) concentrations. Observed relationships of O3 to NOz (NOy–NOx) support past model predictions of increases in cycling of NO and increasing responsiveness of O3 to NOx. The study data provide a long-term record that can be used to examine the accuracy of process relationships embedded in modeling efforts. Quantifying observed O3 trends and relating them to reductions in ambient NOy species concentrations offers key insights into processes of general relevance to air quality management and provides important information supporting strategies for reducing O3 mixing ratios.

Lower tropospheric ozone over India and its linkage to the South Asian monsoon

Abstract. Lower tropospheric (surface to 600 hPa) ozone over India poses serious risks to both human health and crops, and potentially affects global ozone distribution through frequent deep convection in tropical regions. Our current understanding of the processes controlling seasonal and long-term variations in lower tropospheric ozone over this region is rather limited due to spatially and temporally sparse observations. Here we present an integrated process analysis of the seasonal cycle, interannual variability, and long-term trends of lower tropospheric ozone over India and its linkage to the South Asian monsoon using the Ozone Monitoring Instrument (OMI) satellite observations for years 2006–2014 interpreted with a global chemical transport model (GEOS-Chem) simulation for 1990–2010. OMI observed lower tropospheric ozone over India averaged for 2006–2010, showing the highest concentrations (54.1 ppbv) in the pre-summer monsoon season (May) and the lowest concentrations (40.5 ppbv) in the summer monsoon season (August). Process analyses in GEOS-Chem show that hot and dry meteorological conditions and active biomass burning together contribute to 5.8 Tg more ozone being produced in the lower troposphere in India in May than January. The onset of the summer monsoon brings ozone-unfavorable meteorological conditions and strong upward transport, which all lead to large decreases in the lower tropospheric ozone burden. Interannually, we find that both OMI and GEOS-Chem indicate strong positive correlations (r=0.55–0.58) between ozone and surface temperature in pre-summer monsoon seasons, with larger correlations found in high NOx emission regions reflecting NOx-limited production conditions. Summer monsoon seasonal mean ozone levels are strongly controlled by monsoon strengths. Lower ozone concentrations are found in stronger monsoon seasons mainly due to less ozone net chemical production. Furthermore, model simulations over 1990–2010 estimate a mean annual trend of 0.19 ± 0.07 (p value &lt; 0.01) ppbv yr−1 in Indian lower tropospheric ozone over this period, which are mainly driven by increases in anthropogenic emissions with a small contribution (about 7 %) from global methane concentration increases.

Long-term trends of surface ozone and its influencing factors at the Mt Waliguan GAW station, China – Part 2: The roles of anthropogenic emissions and climate variability

Abstract. Inter-annual variability and long-term trends in tropospheric ozone are both environmental and climate concerns. Ozone measured at Mt Waliguan Observatory (WLG, 3816 m a.s.l.) on the Tibetan Plateau over the period of 1994–2013 has increased significantly by 0.2–0.3 ppbv yr−1 during spring and autumn but shows a much smaller trend in winter and no significant trend in summer. Here we explore the factors driving the observed ozone changes at WLG using backward trajectory analysis, chemistry–climate model hindcast simulations (GFDL AM3), a trajectory-mapped ozonesonde data set, and several climate indices. A stratospheric ozone tracer implemented in GFDL AM3 indicates that stratosphere-to-troposphere transport (STT) can explain ∼ 60 % of the simulated springtime ozone increase at WLG, consistent with an increase in the NW air-mass frequency inferred from the trajectory analysis. Enhanced STT associated with the strengthening of the mid-latitude jet stream contributes to the observed high ozone anomalies at WLG during the springs of 1999 and 2012. During autumn, observations at WLG are more heavily influenced by polluted air masses originating from South East Asia than in the other seasons. Rising Asian anthropogenic emissions of ozone precursors are the key driver of increasing autumnal ozone observed at WLG, as supported by the GFDL AM3 model with time-varying emissions, which captures the observed ozone increase (0.26 ± 0.11 ppbv yr−1). AM3 simulates a greater ozone increase of 0.38 ± 0.11 ppbv yr−1 at WLG in autumn under conditions with strong transport from South East Asia and shows no significant ozone trend in autumn when anthropogenic emissions are held constant in time. During summer, WLG is mostly influenced by easterly air masses, but these trajectories do not extend to the polluted regions of eastern China and have decreased significantly over the last 2 decades, which likely explains why summertime ozone measured at WLG shows no significant trend despite ozone increases in eastern China. Analysis of the Trajectory-mapped Ozonesonde data set for the Stratosphere and Troposphere (TOST) and trajectory residence time reveals increases in direct ozone transport from the eastern sector during autumn, which adds to the autumnal ozone increase. We further examine the links of ozone variability at WLG to the quasi-biennial oscillation (QBO), the East Asian summer monsoon (EASM), and the sunspot cycle. Our results suggest that the 2–3-, 3–7-, and 11-year periodicities are linked to the QBO, EASM index, and sunspot cycle, respectively. A multivariate regression analysis is performed to quantify the relative contributions of various factors to surface ozone concentrations at WLG. Through an observational and modelling analysis, this study demonstrates the complex relationships between surface ozone at remote locations and its dynamical and chemical influencing factors.

Trends and sources of ozone and sub-micron aerosols at the Mt. Bachelor Observatory (MBO) during 2004–2015

In this paper, we report the climatology of tropospheric ozone (O3) and sub-micron aerosol scattering at the Mt. Bachelor Observatory (MBO, 2.8 km asl) in central Oregon, USA, during 2004–2015. The seasonal cycle for O3 showed a bimodal pattern with peaks in April and July, while aerosol scattering (σsp) was lognormally distributed with a very high peak in August and a smaller peak in May. The mean O3 concentrations showed positive and significant trends in all seasons except winter, with a slope of 0.6–0.8 ppbv yr−1. Monthly criteria for isolating free tropospheric (FT) and boundary layer influenced (BLI) air masses at MBO were obtained based on comparison of MBO water vapor (WV) distributions to those of Salem (SLE) and Medford (MFR), Oregon, at equivalent pressure level. In all seasons, FT O3 was, on average, higher than BLI O3, but the seasonal patterns were rather similar. For σsp the FT mean in spring was higher, but the BLI mean in summer was significantly higher, indicating the importance of regional wildfire smoke.To better understand the causes for the seasonal and interannual trends at MBO, we identified four major categories of air masses that impact O3, carbon monoxide (CO) and aerosols: upper troposphere and lower stratosphere (UTLS) O3 intrusion, Asian long-range transport (ALRT), Arctic air pollution (AAP) and plumes from the Pacific Northwest region (PNW). ALRT and PNW plumes can be further divided into wildfires (WF), industrial pollution (IP) and mineral dust (MD). Over the 12 years of observations, 177 individual plume events have been identified. Enhancement ratios (ERs) and Ångström exponents (AEs) of aerosols were calculated for all events. The lowest slope of Δσsp/ΔO3 is a unique feature of UTLS events. PNW-WF events have the highest averages for Δσsp/ΔCO, Δσsp/ΔO3 and Δσsp/ΔNOy compared to other events. These ERs decrease during long-range transport due to the shorter residence time of aerosols compared to the other pollutants. ALRT-WF events have lower absorption AEs (Åap) than PNW-WF, implying that brown carbon (BrC) is generated from biomass burning but its fraction decreases during long-range transport. Signatures of ERs and AEs are useful tools to identify different plume categories. These results demonstrate the increasing impact of baseline O3 on US air quality due to both global sources and regional wildfire events.

Regional and hemispheric influences on temporal variability in baseline carbon monoxide and ozone over the Northeast US

Interannual variability in baseline carbon monoxide (CO) and ozone (O3), defined as mixing ratios under minimal influence of recent and local emissions, was studied for seven rural sites in the Northeast US over 2001–2010. Annual baseline CO exhibited statistically significant decreasing trends (−4.3 to −2.3 ppbv yr−1), while baseline O3 did not display trends at any site. In examining the data by season, wintertime and springtime baseline CO at the two highest sites (1.5 km and 2 km asl) did not experience significant trends. Decadal increasing trends (∼2.55 ppbv yr−1) were found in springtime and wintertime baseline O3 in southern New Hampshire, which was associated with anthropogenic NOx emission reductions from the urban corridor. Biomass burning emissions impacted summertime baseline CO with ∼38% variability from wildfire emissions in Russia and ∼22% from Canada at five sites and impacted baseline O3 at the two high elevation sites only with ∼27% variability from wildfires in both Russia and Canada. The Arctic Oscillation was negatively correlated with summertime baseline O3, while the North Atlantic Oscillation was positively correlated with springtime baseline O3. This study suggested that anthropogenic and biomass burning emissions, and meteorological conditions were important factors working together to determine baseline O3 and CO in the Northeast U.S. during the 2000s.

Significant increase of summertime ozone at Mount Tai in Central Eastern China

Abstract. Tropospheric ozone (O3) is a trace gas playing important roles in atmospheric chemistry, air quality and climate change. In contrast to North America and Europe, long-term measurements of surface O3 are very limited in China. We compile available O3 observations at Mt. Tai – the highest mountain over the North China Plain – during 2003–2015 and analyze the decadal change of O3 and its sources. A linear regression analysis shows that summertime O3 measured at Mt. Tai has increased significantly by 1.7 ppbv yr−1 for June and 2.1 ppbv yr−1 for the July–August average. The observed increase is supported by a global chemistry-climate model hindcast (GFDL-AM3) with O3 precursor emissions varying from year to year over 1980–2014. Analysis of satellite data indicates that the O3 increase was mainly due to the increased emissions of O3 precursors, in particular volatile organic compounds (VOCs). An important finding is that the emissions of nitrogen oxides (NOx) have diminished since 2011, but the increase of VOCs appears to have enhanced the ozone production efficiency and contributed to the observed O3 increase in central eastern China. We present evidence that controlling NOx alone, in the absence of VOC controls, is not sufficient to reduce regional O3 levels in North China in a short period.