Tropospheric Ozone Production Research Articles

Ozone production over arid regions: insights into meteorological and chemical drivers

Arid urban areas are pivotal in the global landscape, and their air quality issues are highlighted by the complexities of tropospheric ozone production. Here, we use recent satellite observations from TROPOMI and a longer record of data from OMI to investigate the levels of ozone precursors (NO2 and CH2O) in 12 major cities in arid regions. Using a space-based CH2O/NO2 indicator, we identified the dominant chemical regime influencing ozone formation, revealing a clear temporal trend that aligns with previously reported economic trajectories as well as variation in emission control strategies implemented in these cities. Our results show that, NO2 concentrations decreased in cities with proactive regulatory policies, such as Madrid and Los Angeles in semi-arid and arid regions. A contrasting increase was observed in rapidly developing cities within arid and hyper-arid regions, such as Tehran and Cairo, where emission controls are less strict. An increase in CH2O levels was also apparent, requiring more attention to VOCs control. Furthermore, our analysis clearly shows that the interactions between ozone production and climatic factors such as temperature exhibit a nonlinear relationship, especially in arid climates. These findings highlight the importance of emission reduction strategies that consider the meteorological and chemical drivers of dry regions, particularly in light of the rising global aridity.

Evaluation of isoprene emissions from the coupled model SURFEX–MEGANv2.1

Abstract. Isoprene, a key biogenic volatile organic compound, plays a pivotal role in atmospheric chemistry. Due to its high reactivity, this compound contributes significantly to the production of tropospheric ozone in polluted areas and to the formation of secondary organic aerosols. The assessment of biogenic emissions is of great importance for regional and global air quality evaluation. In this study, we implemented the biogenic emission model MEGANv2.1 (Model of Emissions of Gases and Aerosols from Nature, version 2.1) in the surface model SURFEXv8.1 (SURface EXternalisée in French, version 8.1). This coupling aims to improve the estimation of biogenic emissions using the detailed vegetation-type-dependent treatment included in the SURFEX vegetation ISBA (Interaction between Soil Biosphere and Atmosphere) scheme. This scheme provides vegetation-dependent parameters such as leaf area index and soil moisture to MEGAN. This approach enables a more accurate estimation of biogenic fluxes compared to the stand-alone MEGAN model, which relies on average input values for all vegetation types. The present study focuses on the assessment of the SURFEX–MEGAN model isoprene emissions. An evaluation of the coupled SURFEX–MEGAN model results was carried out by conducting a global isoprene emission simulation in 2019 and by comparing the simulation results with other MEGAN-based isoprene inventories. The coupled model estimates a total global isoprene emission of 443 Tg in 2019. The estimated isoprene is within the range of results obtained with other MEGAN-based isoprene inventories, ranging from 311 to 637 Tg. The spatial distribution of SURFEX–MEGAN isoprene is consistent with other studies, with some differences located in low-isoprene-emission regions. Several sensitivity tests were conducted to quantify the impact of different model inputs and configurations on isoprene emissions. Using different meteorological forcings resulted in a ±5 % change in isoprene emissions using MERRA (Modern-Era Retrospective analysis for Research and Applications) and IFS (Integrated Forecasting System) compared with ERA5. The impact of using different emission factor data was also investigated. The use of PFT (plant functional type) spatial coverage and PFT-dependent emission potential data resulted in a 12 % reduction compared to using the isoprene emission potential gridded map. A significant reduction of around 38 % in global isoprene emissions was observed in the third sensitivity analysis, which applied a parameterization of soil moisture deficit, particularly in certain regions of Australia, Africa, and South America. The significance of coupling the SURFEX and MEGAN models lies particularly in the ability of the coupled model to be forced with meteorological data from any period. This means, for instance, that this system can be used to predict biogenic emissions in the future. This aspect of our work is significant given the changes that biogenic organic compounds are expected to undergo as a result of changes in their climatic factors.

Characterization of tropospheric ozone pollution, random forest trend prediction and analysis of influencing factors in South-western Europe

Nowadays, environmental problems have gradually become the focus of world attention. In recent years, heat waves in many parts of Europe have increased ozone concentrations, fuelling ozone pollution. Therefore, this paper investigates the spatial and temporal distribution of tropospheric column ozone concentrations in South-western Europe, future trend changes, influencing factors, and potential source regions based on remotely sensed monitoring data from the OMI (Ozone Monitoring Instrument) from 2011 to 2021. The results show that the areas of high tropospheric column ozone concentrations are mainly concentrated in the northwest, Poland, and southeast coastal areas. At the same time, the monthly variation curve of column ozone concentration is bimodal. Trend change analyses indicate an upward trend in future column ozone concentrations in the southeastern part of the study area. The potential for increases also exists in parts of Germany, France, and Poland, which will need to be monitored. Random forest model projections found a slight decrease in column ozone concentrations in 2022 and 2023 of about 1–4 DU compared to tropospheric column ozone concentrations in 2021. The health risk assessment found that the number of all-cause premature deaths due to exposure to ozone was the highest in Germany. During the summer, when ozone pollution is high, the potential source area in the southeastern part of the study area is located at the border of the three countries, and synergistic management is recommended. In exploring the correlation between the influencing factors and ozone, it was found that there is a significant difference between the long-time and short-time series. In addition, the pathway analysis shows that the population size, distribution density, and forested area in southwestern Europe may be more sensitive to the production of tropospheric ozone.

Elevated tropospheric ozone and crop production: potential negative effects and plant defense mechanisms.

Ozone (O3) levels on Earth are increasing because of anthropogenic activities and natural processes. Ozone enters plants through the leaves, leading to the overgeneration of reactive oxygen species (ROS) in the mesophyll and guard cell walls. ROS can damage chloroplast ultrastructure and block photosynthetic electron transport. Ozone can lead to stomatal closure and alter stomatal conductance, thereby hindering carbon dioxide (CO2) fixation. Ozone-induced leaf chlorosis is common. All of these factors lead to a reduction in photosynthesis under O3 stress. Long-term exposure to high concentrations of O3 disrupts plant physiological processes, including water and nutrient uptake, respiration, and translocation of assimilates and metabolites. As a result, plant growth and reproductive performance are negatively affected. Thus, reduction in crop yield and deterioration of crop quality are the greatest effects of O3 stress on plants. Increased rates of hydrogen peroxide accumulation, lipid peroxidation, and ion leakage are the common indicators of oxidative damage in plants exposed to O3 stress. Ozone disrupts the antioxidant defense system of plants by disturbing enzymatic activity and non-enzymatic antioxidant content. Improving photosynthetic pathways, various physiological processes, antioxidant defense, and phytohormone regulation, which can be achieved through various approaches, have been reported as vital strategies for improving O3 stress tolerance in plants. In plants, O3 stress can be mitigated in several ways. However, improvements in crop management practices, CO2 fertilization, using chemical elicitors, nutrient management, and the selection of tolerant crop varieties have been documented to mitigate O3 stress in different plant species. In this review, the responses of O3-exposed plants are summarized, and different mitigation strategies to decrease O3 stress-induced damage and crop losses are discussed. Further research should be conducted to determine methods to mitigate crop loss, enhance plant antioxidant defenses, modify physiological characteristics, and apply protectants.

Determination of Ozone Concentration Levels in Urban Environments Using a Laser Spectroscopy System

In urban areas, there has been a recent rise in ground-level ozone. Given its toxicity to both humans and the environment, the investigation of ozone pollution demands attention and should not be overlooked. Therefore, we conducted a study on ozone concentration in three distinct locations within the city of Magurele, Romania. This investigation considered variations in both structure and location during the spring and summer seasons, specifically at a breathing level of 1.5 m above the ground. Our analysis aimed to explore the impact of different locations and meteorological variables on ozone levels. The three measurement points were strategically positioned in diverse settings: within the city, in a forest, and within an industrial area. For these measurements, we used a laser spectroscopy system to determine the system’s sensitivity and selectivity and the influence of humidity in the detection of ozone in ambient air, which is a mixture of trace gases and water vapor. During the March–August campaign, the mean values in the three measuring points were 24.45 ± 16.44 ppb, 11.96 ± 3.80 ppb, and 95.01 ± 37.11 ppb. The peak concentrations of ozone were observed during the summer season. A diurnal analysis revealed that the atmospheric ozone levels were higher in the latter part of the day compared to the earlier part. These measurements suggest that the atmospheric temperature plays a significant role in tropospheric ozone production. Additionally, meteorological variables such as wind speed and direction were found to influence the ozone concentration. Remarkably, despite substantial traffic, the ozone levels remained consistently low throughout the entire period within the forested area. This observation may suggest the remarkable ability of trees to mitigate pollution levels.

Development and application of a nitrogen oxides analyzer based on the cavity attenuated phase shift technique

Nitrogen oxides (NOx) are crucial in tropospheric photochemical ozone (O3) production and oxidation capacity. Currently, the widely used NOx measurement technique is chemiluminescence (CL) (CL-NOx), which tends to overestimate NO2 due to atmospheric oxidation products of NOx (i.e., NOz). We developed and characterized a NOx measurement system using the cavity attenuated phase shift (CAPS) technique (CAPS-NOx), which is free from interferences with nitrogen-containing species. The NOx measured by the CAPS-NOx and CL-NOx analyzers were compared. Results show that both analyzers showed consistent measurement results for NO, but the NO2 measured by the CAPS-NOx analyzer (NO2_CAPS) was mostly lower than that measured by the CL-NOx analyzer (NO2_CL), which led to the deviations in O3 formation sensitivity regime and Ox (= O3 + NO2) sources (i.e., regional background and photochemically produced Ox) determined by the ozone production efficiencies (OPE) calculated from NO2_CL and NO2_CAPS. Overall, OPE_CL exceeded OPE_CAPS by 18.9%, which shifted 3 out of 13 observation days from the VOCs-limited to the transition regime when judging using OPE_CL, as compared to calculations using OPE_CAPS. During the observation period, days dominated by regional background Ox accounted for 46% and 62% when determined using NO2_CL and NO2_CAPS, respectively. These findings suggest that the use of the CL-NOx analyzer tends to underestimate both the VOCs-limited regime and the regional background Ox dominated days. The newly built CAPS-NOx analyzer here can promote the accurate measurement of NO2, which is meaningful for diagnosing O3 formation regimes and Ox sources.

Determination of BVOCs based on high time-resolved measurements in urban and forest areas in Japan

Biogenic volatile organic compounds (BVOCs) with high photochemical activity and short atmospheric lifetimes are major contributors to tropospheric ozone and other photochemical air pollution. Although several studies have been conducted on BVOC emissions in Japan, no comprehensive observations have been made to determine the actual state of BVOCs in the atmosphere. Therefore, we conducted time-resolved measurements of atmospheric BVOCs in urban and forested areas throughout the year. The concentrations of BVOCs were higher in summer than in the other seasons. Isoprene concentrations were higher during hours with higher temperatures and solar radiation. However, there were also months and times of the year when monoterpenes showed high concentrations, which indicates that the behavior of the BVOC components differed depending on the time of the year. The results of the propylene equivalent concentration indicated that BVOCs considerably contributed to tropospheric ozone production. The year-long observations of BVOCs in this study contribute to our understanding of the actual status of atmospheric BVOC concentrations and components and the uncertainty in the calculation results of chemical transport models.

Changes in tropospheric air quality related to the protection of stratospheric ozone in a changing climate

Ultraviolet (UV) radiation drives the net production of tropospheric ozone (O3) and a large fraction of particulate matter (PM) including sulfate, nitrate, and secondary organic aerosols. Ground-level O3 and PM are detrimental to human health, leading to several million premature deaths per year globally, and have adverse effects on plants and the yields of crops. The Montreal Protocol has prevented large increases in UV radiation that would have had major impacts on air quality. Future scenarios in which stratospheric O3 returns to 1980 values or even exceeds them (the so-called super-recovery) will tend to ameliorate urban ground-level O3 slightly but worsen it in rural areas. Furthermore, recovery of stratospheric O3 is expected to increase the amount of O3 transported into the troposphere by meteorological processes that are sensitive to climate change. UV radiation also generates hydroxyl radicals (OH) that control the amounts of many environmentally important chemicals in the atmosphere including some greenhouse gases, e.g., methane (CH4), and some short-lived ozone-depleting substances (ODSs). Recent modeling studies have shown that the increases in UV radiation associated with the depletion of stratospheric ozone over 1980–2020 have contributed a small increase (~ 3%) to the globally averaged concentrations of OH. Replacements for ODSs include chemicals that react with OH radicals, hence preventing the transport of these chemicals to the stratosphere. Some of these chemicals, e.g., hydrofluorocarbons that are currently being phased out, and hydrofluoroolefins now used increasingly, decompose into products whose fate in the environment warrants further investigation. One such product, trifluoroacetic acid (TFA), has no obvious pathway of degradation and might accumulate in some water bodies, but is unlikely to cause adverse effects out to 2100.Graphical abstract

Ground-Based MAX-DOAS Observation of Trace Gases from 2019 to 2021 in Huaibei, China

With the spread of the COVID-19 pandemic and the implementation of closure measures in 2020, population mobility and human activities have decreased, which has seriously impacted atmospheric quality. Huaibei City is an important coal and chemical production base in East China, which faces increasing environmental problems. The impact of anthropogenic activities on air quality in this area was investigated by comparing the COVID-19 lockdown in 2020 with the normal situation in 2021. Tropospheric NO2, HCHO and SO2 column densities were observed by ground-based multiple axis differential optical absorption spectroscopy (MAX-DOAS). In situ measurements for PM2.5, NO2, SO2 and O3 were also taken. The observation period was divided into four phases, the pre-lockdown period, phase 1 lockdown, phase 2 lockdown and the post-lockdown period. Ground-based MAX-DOAS results showed that tropospheric NO2, HCHO and SO2 column densities increased by 41, 14 and 14%, respectively, during phase 1 in 2021 vs. 2020. In situ results showed that NO2 and SO2 increased by 59 and 11%, respectively, during phase 1 in 2021 vs. 2020, but PM2.5 and O3 decreased by 15 and 17%, respectively. In the phase 2 period, due to the partial lifting of control measures, the concentration of pollutants did not significantly change. The weekly MAX-DOAS results showed that there was no obvious weekend effect of pollutants in the Huaibei area, and NO2, HCHO and SO2 had obvious diurnal variation characteristics. In addition, the relationship between the column densities and wind speed and direction in 2020 and 2021 was studied. The results showed that, in the absence of traffic control in 2021, elevated sources in the Eastern part of the city emitted large amounts of NO2. The observed ratios of HCHO to NO2 suggested that tropospheric ozone production involved NOX-limited scenarios. The correlation analysis between HCHO and different gases showed that HCHO mainly originated from primary emission sources related to SO2.

Synergy of Using Nadir and Limb Instruments for Tropospheric Ozone Monitoring (SUNLIT)

Abstract. Satellite measurements in nadir and limb viewing geometry provide a complementary view of the atmosphere. An effective combination of the limb and nadir measurements can give new information about atmospheric composition. In this work, we present tropospheric ozone column datasets that have been created using a combination of total ozone columns from OMI (Ozone Monitoring Instrument) and TROPOMI (TROPOspheric Monitoring Instrument) with stratospheric ozone column datasets from several available limb-viewing instruments: MLS (Microwave Limb Sounder), OSIRIS (Optical Spectrograph and InfraRed Imaging System), MIPAS (Michelson Interferometer for Passive Atmospheric Sounding), SCIAMACHY (SCanning Imaging Spectrometer for Atmospheric CHartographY), OMPS-LP (Ozone Mapping and Profiles Suite – Limb Profiler), and GOMOS (Global Ozone Monitoring by Occultation of Stars). We have developed further the methodological aspects of the assessment of tropospheric ozone using the residual method supported by simulations with the chemistry transport model SILAM (System for Integrated modeLling of Atmospheric coMposition). It has been shown that the accurate assessment of ozone in the upper troposphere and the lower stratosphere (UTLS) is of high importance for detecting the ground-level ozone patterns. The stratospheric ozone column is derived from a combination of ozone profiles from several satellite instruments in limb-viewing geometry. We developed a method for the data homogenization, which includes the removal of biases and a posteriori estimation of random uncertainties, thus making the data from different instruments compatible with each other. The high-horizontal- and vertical-resolution dataset of ozone profiles is created via interpolation of the limb profiles from each day to a 1∘×1∘ horizonal grid. A new kriging-type interpolation method, which takes into account data uncertainties and the information about natural ozone variations from the SILAM-adjusted ozone field, has been developed. To mitigate the limited accuracy and coverage of the limb profile data in the UTLS, a smooth transition to the model data is applied below the tropopause. This allows for the estimation of the stratospheric ozone column with full coverage of the UTLS. The derived ozone profiles are in very good agreement with collocated ozonesonde measurements. The residual method was successfully applied to OMI and TROPOMI clear-sky total ozone data in combination with the stratospheric ozone column from the developed high-resolution limb profile dataset. The resulting tropospheric ozone column is in very good agreement with other satellite data. The global distributions of tropospheric ozone exhibit enhancements associated with the regions of high tropospheric ozone production. The main datasets created are (i) a monthly 1∘×1∘ global tropospheric ozone column dataset (from ground to 3 km below the tropopause) using OMI and limb instruments, (ii) a monthly 1∘×1∘ global tropospheric ozone column dataset using TROPOMI and limb instruments, and (iii) a daily 1∘×1∘ interpolated stratospheric ozone column from limb instruments. Other datasets, which are created as an intermediate step of creating the tropospheric ozone column data, are (i) a daily 1∘×1∘ clear-sky and total ozone column from OMI and TROPOMI, (ii) a daily 1∘×1∘ homogenized and interpolated dataset of ozone profiles from limb instruments, and (iii) a daily 1∘×1∘ dataset of ozone profiles from SILAM simulations with adjustment to satellite data. These datasets can be used in various studies related to variability and trends in ozone distributions in both the troposphere and the stratosphere. The datasets are processed from the beginning of OMI and TROPOMI measurements until December 2020 and are planned to be regularly extended in the future.

Stratosphere‐Troposphere Exchanges of Air Mass and Ozone Concentration in the Last Glacial Maximum

AbstractStratosphere‐troposphere exchange (STE) of ozone represents a significant source term in the tropospheric ozone budget and can impact surface ozone concentrations, tropospheric oxidation capacity, and methane lifetime. Using the Whole Atmosphere Community Climate Model 6, changes in the air mass and ozone STEs in the Last Glacial Maximum (LGM) as compared with preindustrial (PI) climate are investigated. We use dynamic isentropic surfaces that are determined by fitting to the tropical tropopauses as the upper boundary of the lowermost stratosphere in a mass budget approach, a method particularly suitable for estimating air mass and ozone STEs across different climates. Relative to the PI, the magnitude of ozone STE in the LGM is decreased by 14%–19%, 18%–24%, 18%–23%, 16%–21%, and 15%–21% over the Northern hemisphere extratropics, Southern hemisphere extratropics, the tropics, the extratropics, and the globe, respectively. The extratropical and global decreases are mainly caused by decreased ozone in the extratropical lower stratosphere associated with a weakening of Brewer‐Dobson circulation, while changes in air mass fluxes play a minor role because the effects of weakening Brewer‐Dobson circulation and increased isentropic density partly cancel each other. Analysis of the modeled tropospheric ozone budget indicates that the ozone STE in the LGM is 28% of the tropospheric ozone production rate, as compared to about 9% in the modern climate (year 2000) and 19% in the PI.

Tropospheric ozone production and chemical regime analysis during the COVID-19 lockdown over Europe

Abstract. The COVID-19 (coronavirus disease 2019) European lockdowns have led to a significant reduction in the emissions of primary pollutants such as NO (nitric oxide) and NO2 (nitrogen dioxide). As most photochemical processes are related to nitrogen oxide (NOx≡ NO + NO2) chemistry, this event has presented an exceptional opportunity to investigate its effects on air quality and secondary pollutants, such as tropospheric ozone (O3). In this study, we present the effects of the COVID-19 lockdown on atmospheric trace gas concentrations, net ozone production rates (NOPRs) and the dominant chemical regime throughout the troposphere based on three different research aircraft campaigns across Europe. These are the UTOPIHAN (Upper Tropospheric Ozone: Processes Involving HOx and NOx) campaigns in 2003 and 2004, the HOOVER (HOx over Europe) campaigns in 2006 and 2007, and the BLUESKY campaign in 2020, the latter performed during the COVID-19 lockdown. We present in situ observations and simulation results from the ECHAM5 (fifth-generation European Centre Hamburg general circulation model, version 5.3.02)/MESSy2 (second-generation Modular Earth Submodel System, version 2.54.0) Atmospheric Chemistry (EMAC), model which allows for scenario calculations with business-as-usual emissions during the BLUESKY campaign, referred to as the “no-lockdown scenario”. We show that the COVID-19 lockdown reduced NO and NO2 mixing ratios in the upper troposphere by around 55 % compared to the no-lockdown scenario due to reduced air traffic. O3 production and loss terms reflected this reduction with a deceleration in O3 cycling due to reduced mixing ratios of NOx, while NOPRs were largely unaffected. We also study the role of methyl peroxyradicals forming HCHO (αCH3O2) to show that the COVID-19 lockdown shifted the chemistry in the upper-troposphere–tropopause region to a NOx-limited regime during BLUESKY. In comparison, we find a volatile organic compound (VOC)-limited regime to be dominant during UTOPIHAN.

Leaf-Scale Study of Biogenic Volatile Organic Compound Emissions from Willow (Salix spp.) Short Rotation Coppices Covering Two Growing Seasons

In Europe, willow (Salix spp.) trees have been used commercially since the 1980s at a large scale to produce renewable energy. While reducing fossil fuel needs, growing short rotation coppices (SRCs), such as poplar or willow, may have a high impact on local air quality as these species are known to produce high amounts of isoprene, which can lead to the production of tropospheric ozone (O3). Here, we present a long-term leaf-scale study of biogenic volatile organic compound (BVOC) emissions from a Swedish managed willow site with the aim of providing information on the seasonal variability in BVOC emissions during two growing seasons, 2015–2016. Total BVOC emissions during these two seasons were dominated by isoprene (>96% by mass) and the monoterpene (MT) ocimene. The average standardized (STD, temperature of 30 °C and photosynthetically active radiation of 1000 µmol m−2 s−1) emission rate for isoprene was 45.2 (±42.9, standard deviation (SD)) μg gdw−1 h−1. Isoprene varied through the season, mainly depending on the prevailing temperature and light, where the measured emissions peaked in July 2015 and August 2016. The average STD emission for MTs was 0.301 (±0.201) μg gdw−1 h−1 and the MT emissions decreased from spring to autumn. The average STD emission for sesquiterpenes (SQTs) was 0.103 (±0.249) μg gdw−1 h−1, where caryophyllene was the most abundant SQT. The measured emissions of SQTs peaked in August both in 2015 and 2016. Non-terpenoid compounds were grouped as other VOCs (0.751 ± 0.159 μg gdw−1 h−1), containing alkanes, aldehydes, ketones, and other compounds. Emissions from all the BVOC groups decreased towards the end of the growing season. The more sun-adapted leaves in the upper part of the plantation canopy emitted higher rates of isoprene, MTs, and SQTs compared with more shade-adapted leaves in the lower canopy. On the other hand, emissions of other VOCs were lower from the upper part of the canopy compared with the lower part. Light response curves showed that ocimene and α-farnesene increased with light but only for the sun-adapted leaves, since the shade-adapted leaves did not emit ocimene and α-farnesene. An infestation with Melampsora spp. likely induced high emissions of, e.g., hexanal and nonanal in August 2015. The results from this study imply that upscaling BVOC emissions with model approaches should account for seasonality and also include the canopy position of leaves as a parameter to allow for better estimates for the regional and global budgets of ecosystem emissions.

The role of tropospheric ozone in flagging COVID-19 pandemic transmission.

COVID-19 pandemic outbreak, caused by the SARS-CoV-2 virus, affected millions of people worldwide causing hundreds of thousands of related fatalities. It is crucial to understand why the virus transmission seems to spread more easily in some regions than others. The residuals, with respect to the modeled COVID-19 per-day hospitalized patients in intensive care unit, are correlated to the meteorological and air-pollutant variables in four major metropolitan areas in Italy during a strict lockdown implemented by the Italian government, making the analysis independent from socio-economic factors. The results show that COVID-19 pandemic–related infections are slowed down by higher tropospheric ozone concentrations and eased by the atmospheric particulate. We quantitatively assessed that higher levels of tropospheric ozone, already proven effective against viruses and microbial contaminants, play a role in flagging COVID-19 pandemic transmission. Because the tropospheric ozone production is depending, among others, by air-quality and sunlight, this can explain why the virus is spreading in different ways.

Investigating the Impacts of the COVID-19 Lockdown on Trace Gases Using Ground-Based MAX-DOAS Observations in Nanjing, China

The spread of the COVID-19 pandemic and consequent lockdowns all over the world have had various impacts on atmospheric quality. This study aimed to investigate the impact of the lockdown on the air quality of Nanjing, China. The off-axis measurements from state-of-the-art remote-sensing Multi-Axis Differential Optical Absorption Spectroscope (MAX-DOAS) were used to observe the trace gases, i.e., Formaldehyde (HCHO), Nitrogen Dioxide (NO2), and Sulfur Dioxide (SO2), along with the in-situ time series of NO2, SO2 and Ozone (O3). The total dataset covers the span of five months, from 1 December 2019, to 10 May 2020, which comprises of four phases, i.e., the pre lockdown phase (1 December 2019, to 23 January 2020), Phase-1 lockdown (24 January 2020, to 26 February 2020), Phase-2 lockdown (27 February 2020, to 31 March 2020), and post lockdown (1 April 2020, to 10 May 2020). The observed results clearly showed that the concentrations of selected pollutants were lower along with improved air quality during the lockdown periods (Phase-1 and Phase-2) with only the exception of O3, which showed an increasing trend during lockdown. The study concluded that limited anthropogenic activities during the spring festival and lockdown phases improved air quality with a significant reduction of selected trace gases, i.e., NO2 59%, HCHO 38%, and SO2 33%. We also compared our results with 2019 data for available gases. Our results imply that the air pollutants concentration reduction in 2019 during Phase-2 was insignificant, which was due to the business as usual conditions after the Spring Festival (Phase-1) in 2019. In contrast, a significant contamination reduction was observed during Phase-2 in 2020 with the enforcement of a Level-II response in lockdown conditions i.e., the easing of the lockdown situation in some sectors during a specific interval of time. The observed ratio of HCHO to NO2 showed that tropospheric ozone production involved Volatile Organic Compounds (VOC) limited scenarios.

Surface ozone exceedances in Melbourne, Australia are shown to be under NOx control, as demonstrated using formaldehyde:NO2 and glyoxal:formaldehyde ratios

Two and a half years of multi-axis differential optical absorption spectroscopy (MAX-DOAS) measurements of nitrogen dioxide (NO2), formaldehyde (HCHO) and glyoxal (CHOCHO) are presented alongside in-situ ozone (O3) measurements in Melbourne, Australia. Seasonal and diurnal cycles, vertical profiles and relationships with key meteorological variables are provided. NO2 and CHOCHO were found at highest concentration for low wind speeds implying that their sources were predominantly localised and anthropogenic. HCHO showed an exponential relationship with temperature and a strong wind direction dependence from the northern and eastern sectors, and therefore most likely originated from oxidation of biogenic volatile organic compounds (VOCs) from surrounding forested and rural areas. The glyoxal:formaldehyde ratio (Rgf), reported for the first time in Australia, was consistently high compared to values elsewhere in the world with a mean of 0.105 ± 0.0503 and tended to increase with increasing anthropogenic influence. The HCHO:NO2 ratio (Rfn) was used to characterise tropospheric ozone formation conditions. A strong relationship was found between high temperature, low Rgf, high Rfn and high ozone surface concentrations. Therefore, we propose that both Rgf and Rfn may be useful indicators of tropospheric ozone production regimes and concentrations. The Rfn showed that the vast majority of high ozone production episodes occurred under NOx-limited conditions, suggesting that surface ozone pollution events in Melbourne could be curtailed using NOx emission controls.

On the Changing Role of the Stratosphere on the Tropospheric Ozone Budget: 1979–2010

AbstractWe study the evolution of tropospheric ozone over the period 1979–2010 using a chemistry‐climate model employing a stratosphere‐troposphere chemistry scheme. By running with specified dynamics, the key feedback of composition on meteorology is suppressed, isolating the chemical response. By using historical forcings and emissions, interactions between processes are realistically represented. We use the model to assess how the ozone responds over time and to investigate model responses and trends. We find that the chlorofluorocarbon (CFC)‐driven decrease in stratospheric ozone plays a significant role in the tropospheric ozone burden. Over the period 1979–1994, the decline in transport of ozone from the stratosphere, partially offsets an emissions‐driven increase in tropospheric ozone production. From 1994–2010, despite a leveling off in emissions, increased stratosphere‐to‐troposphere transport of ozone drives a small increase in the tropospheric ozone burden. These results have implications for the impact of future stratospheric ozone recovery on air quality and radiative forcing.

High productivity in hybrid-poplar plantations without isoprene emission to the atmosphere

Hybrid-poplar tree plantations provide a source for biofuel and biomass, but they also increase forest isoprene emissions. The consequences of increased isoprene emissions include higher rates of tropospheric ozone production, increases in the lifetime of methane, and increases in atmospheric aerosol production, all of which affect the global energy budget and/or lead to the degradation of air quality. Using RNA interference (RNAi) to suppress isoprene emission, we show that this trait, which is thought to be required for the tolerance of abiotic stress, is not required for high rates of photosynthesis and woody biomass production in the agroforest plantation environment, even in areas with high levels of climatic stress. Biomass production over 4 y in plantations in Arizona and Oregon was similar among genetic lines that emitted or did not emit significant amounts of isoprene. Lines that had substantially reduced isoprene emission rates also showed decreases in flavonol pigments, which reduce oxidative damage during extremes of abiotic stress, a pattern that would be expected to amplify metabolic dysfunction in the absence of isoprene production in stress-prone climate regimes. However, compensatory increases in the expression of other proteomic components, especially those associated with the production of protective compounds, such as carotenoids and terpenoids, and the fact that most biomass is produced prior to the hottest and driest part of the growing season explain the observed pattern of high biomass production with low isoprene emission. Our results show that it is possible to reduce the deleterious influences of isoprene on the atmosphere, while sustaining woody biomass production in temperate agroforest plantations.

Mechanistic study of the formation of ring-retaining and ring-opening products from the oxidation of aromatic compounds under urban atmospheric conditions.

Aromatic hydrocarbons make up a large fraction of anthropogenic volatile organic compounds and contribute significantly to the production of tropospheric ozone and secondary organic aerosol (SOA). Four toluene and four 1,2,4-trimethylbenzene (1,2,4-TMB) photooxidation experiments were performed in an environmental chamber under relevant polluted conditions (NO x ~ 10ppb). An extensive suite of instrumentation including two proton-transfer-reaction mass spectrometers (PTR-MS) and two chemical ionisation mass spectrometers ( CIMS and I- CIMS) allowed for quantification of reactive carbon in multiple generations of hydroxyl radical (OH)-initiated oxidation. Oxidation of both species produces ring-retaining products such as cresols, benzaldehydes, and bicyclic intermediate compounds, as well as ring-scission products such as epoxides and dicarbonyls. We show that the oxidation of bicyclic intermediate products leads to the formation of compounds with high oxygen content (an O : C ratio of up to 1.1). These compounds, previously identified as highly oxygenated molecules (HOMs), are produced by more than one pathway with differing numbers of reaction steps with OH, including both auto-oxidation and phenolic pathways. We report the elemental composition of these compounds formed under relevant urban high-NO conditions. We show that ring-retaining products for these two precursors are more diverse and abundant than predicted by current mechanisms. We present the speciated elemental composition of SOA for both precursors and confirm that highly oxygenated products make up a significant fraction of SOA. Ring-scission products are also detected in both the gas and particle phases, and their yields and speciation generally agree with the kinetic model prediction.

Sensitive Detection of Gas-Phase Glyoxal by Electron Attachment Reaction Ionization Mass Spectrometry.

Glyoxal (GLY) acts as a key contributor to tropospheric ozone production and secondary organic aerosol (SOA) formation on local to regional scales. The detection of GLY provides useful indicators of fast photochemistry occurring in the lower troposphere. The fast and sensitive detection of GLY is thus important, while traditional chemical ionization such as the proton-transfer reaction (PTR) is extremely limited by the poor detection limit and extensive fragmentation. To address these limitations, electron attachment reaction (EAR) ionization was applied to detect GLY. The generation of parent anions (GLY-) without fragmentation was observed, and cryogenic photoelectron imaging spectroscopy further characterized the structure of GLY-. The detection limit was estimated to be as low as (52 ± 1) pptv (parts per trillion by volume) with 1 min measurements. Other components in ambient air, such as water, carbon dioxide, and trace gases (acetone, propanal, etc.) have no effect on the detection of GLY. The EAR ionization is more promising than PTR ionization in detecting GLY. The detection of GLY in ambient air by the EAR ionization has been demonstrated.