Source Of Tropospheric Ozone Research Articles

All-cause, cardiovascular, and respiratory mortality and wildfire-related ozone: a multicountry two-stage time series analysis

Wildfire activity is an important source of tropospheric ozone (O3) pollution. However, no study to date has systematically examined the associations of wildfire-related O3 exposure with mortality globally. We did a multicountry two-stage time series analysis. From the Multi-City Multi-Country (MCC) Collaborative Research Network, data on daily all-cause, cardiovascular, and respiratory deaths were obtained from 749 locations in 43 countries or areas, representing overlapping periods from Jan 1, 2000, to Dec 31, 2016. We estimated the daily concentration of wildfire-related O3 in study locations using a chemical transport model, and then calibrated and downscaled O3 estimates to a resolution of 0·25° × 0·25° (approximately 28 km2 at the equator). Using a random-effects meta-analysis, we examined the associations of short-term wildfire-related O3 exposure (lag period of 0-2 days) with daily mortality, first at the location level and then pooled at the country, regional, and global levels. Annual excess mortality fraction in each location attributable to wildfire-related O3 was calculated with pooled effect estimates and used to obtain excess mortality fractions at country, regional, and global levels. Between 2000 and 2016, the highest maximum daily wildfire-related O3 concentrations (≥30 μg/m3) were observed in locations in South America, central America, and southeastern Asia, and the country of South Africa. Across all locations, an increase of 1 μg/m3 in the mean daily concentration of wildfire-related O3 during lag 0-2 days was associated with increases of 0·55% (95% CI 0·29 to 0·80) in daily all-cause mortality, 0·44% (-0·10 to 0·99) in daily cardiovascular mortality, and 0·82% (0·18 to 1·47) in daily respiratory mortality. The associations of daily mortality rates with wildfire-related O3 exposure showed substantial geographical heterogeneity at the country and regional levels. Across all locations, estimated annual excess mortality fractions of 0·58% (95% CI 0·31 to 0·85; 31 606 deaths [95% CI 17 038 to 46 027]) for all-cause mortality, 0·41% (-0·10 to 0·91; 5249 [-1244 to 11 620]) for cardiovascular mortality, and 0·86% (0·18 to 1·51; 4657 [999 to 8206]) for respiratory mortality were attributable to short-term exposure to wildfire-related O3. In this study, we observed an increase in all-cause and respiratory mortality associated with short-term wildfire-related O3 exposure. Effective risk and smoke management strategies should be implemented to protect the public from the impacts of wildfires. Australian Research Council and the Australian National Health and Medical Research Council.

The Stratosphere-to-Troposphere Transport Related to Rossby Wave Breaking and Its Impact on Summertime Ground-Level Ozone in Eastern China

In summertime, eastern China experiences severe ozone pollution. Stratosphere-to-troposphere transport (STT), as the primary natural source of tropospheric ozone, may have a non-negligible contribution to ground-level ozone. Rossby wave breaking (RWB) is a leading mechanism that triggers STT, which can be categorized as anticyclonic wave breakings (AWBs) and cyclonic wave breakings (CWBs). This study uses an objective method to diagnose AWBs and CWBs and to investigate their influence on the surface ozone in eastern China using ground-based ozone observations, satellite ozone data from AIRS, a stratospheric ozone tracer simulated by CAM-chem, and meteorological fields from MERRA-2. The results indicate that AWBs occur mainly and frequently over northeast China, while CWBs occur mostly over the northern Sea of Japan. STTs triggered by AWBs mainly have sinking areas over the North China Plain, increasing the ground-level ozone concentrations by 5–10 ppbv in eastern China. The downwelling zones in the CWBs extend from Mongolia to the East China Sea, potentially causing an elevation of 5–10 ppbv of ozone in both central and eastern China. This study gives an overview of the impacts of AWBs and CWBs on surface ozone in eastern China and helps to improve our understanding of summertime ozone pollution in eastern China.

Stratospheric intrusion may aggravate widespread ozone pollution through both vertical and horizontal advections in eastern China during summer

Stratospheric intrusion (SI) is an important source of tropospheric ozone (O3). Here, we used the online coupled Weather Research and Forecasting-Chemistry (WRF-Chem) model to simulate a typical SI event that occurred over eastern China on 15–19 July 2016 and investigate the impacts of SI on near-surface O3 pollution. The results show that the large-scale circulation of SI was characterized by a deep trough over central China and South Asia high and Western Pacific Subtropical high located to the east and west of the deep trough, respectively. With the evolution of the deep trough, the strong downdrafts behind the trough lead to O3-rich air injected into the lower troposphere across eastern China. By using a tracer tagging method in WRF-Chem, we quantified the SI contributed up to 6.5 ppb to the surface O3 concentration. According to the integrated process rate analyses, which were employed to quantify the contribution of different physical/chemical processes to O3, the advection process dominated variations in troposphere O3 with positive contribution ranging from 0.1 to 13.8 ppb h−1. As altitude decreases, the contribution of advection diminishes as the intensity of the SI gradually weakens. Although the vertical advection contributed limited O3 that directly reached the ground, we revealed that the SI has significant impact on near-surface O3 over a large territory of eastern China through regional transport by horizontal advection process. Below 691 m, the positive contribution of horizontal advection to O3 ranges from 1.6 to 13.4 ppb h−1. This study highlights the natural effect of SI on summertime O3 pollution in eastern China and will help the development of a future O3 pollution alert system.

Transport of substantial stratospheric ozone to the surface by a dying typhoon and shallow convection

Abstract. Stratospheric ozone transported to the troposphere is estimated to account for 5 %–15 % of the tropospheric ozone sources. However, the chances of intruded stratospheric ozone reaching the surface are low. Here, we report an event of a strong surface ozone surge of stratospheric origin in the North China Plain (NCP, 34–40∘ N, 114–121∘ E) during the night of 31 July 2021. The hourly measurements reveal surface ozone concentrations of up to 80–90 ppbv at several cities over the NCP from 23:00 LST (Local Standard time, = UTC +8 h) on 31 July to 06:00 LST on 1 August 2021. The ozone enhancement was 40–50 ppbv higher than the corresponding monthly mean. A high-frequency surface measurement indicates that this ozone surge occurred abruptly, with an increase reaching 40–50 ppbv within 10 min. A concurrent decline in surface carbon monoxide (CO) concentrations suggests that this surface ozone surge might have resulted from the downward transport of a stratospheric ozone-rich and CO-poor air mass. This is further confirmed by the vertical evolutions of humidity and ozone profiles based on radiosonde and satellite data respectively. Such an event of stratospheric impact on surface ozone is rarely documented in view of its magnitude, coverage, and duration. We find that this surface ozone surge was induced by a combined effect of dying Typhoon In-fa and shallow local mesoscale convective systems (MCSs) that facilitated transport of stratospheric ozone to the surface. This finding is based on analysis of meteorological reanalysis and radiosonde data, combined with high-resolution Weather Research and Forecasting (WRF) simulation and backward trajectory analysis using the FLEXible PARTicle (FLEXPART) particle dispersion model. Although Typhoon In-fa on the synoptic scale was at its dissipation stage when it passed through the NCP, it could still bring down a stratospheric dry and ozone-rich air mass. As a result, the stratospheric air mass descended to the middle-to-low troposphere over the NCP before the MCSs formed. With the pre-existing stratospheric air mass, the convective downdrafts of the MCSs facilitated the final descent of stratospheric air mass to the surface. Significant surface ozone enhancement occurred in the convective downdraft regions during the development and propagation of the MCSs. This study underscores the substantial roles of weak convection in transporting stratospheric ozone to the lower troposphere and even to the surface, which has important implications for air quality and climate change.

From the middle stratosphere to the surface, using nitrous oxide to constrain the stratosphere–troposphere exchange of ozone

Abstract. Stratosphere–troposphere exchange (STE) is an important source of tropospheric ozone, affecting all of atmospheric chemistry, climate, and air quality. The study of impacts needs STE fluxes to be resolved by latitude and month, and for this, we rely on global chemistry models, whose results diverge greatly. Overall, we lack guidance from model–measurement metrics that inform us about processes and patterns related to the STE flux of ozone (O3). In this work, we use modeled tracers (N2O and CFCl3), whose distributions and budgets can be constrained by satellite and surface observations, allowing us to follow stratospheric signals across the tropopause. The satellite-derived photochemical loss of N2O on annual and quasi-biennial cycles can be matched by the models. The STE flux of N2O-depleted air in our chemistry transport model drives surface variability that closely matches observed fluctuations on both annual and quasi-biennial cycles, confirming the modeled flux. The observed tracer correlations between N2O and O3 in the lowermost stratosphere provide a hemispheric scaling of the N2O STE flux to that of O3. For N2O and CFCl3, we model greater southern hemispheric STE fluxes, a result supported by some metrics, but counter to the prevailing theory of wave-driven stratospheric circulation. The STE flux of O3, however, is predominantly northern hemispheric, but evidence shows that this is caused by the Antarctic ozone hole reducing southern hemispheric O3 STE by 14 %. Our best estimate of the current STE O3 flux based on a range of constraints is 400 Tg(O3) yr−1, with a 1σ uncertainty of ±15 % and with a NH : SH ratio ranging from 50:50 to 60:40. We identify a range of observational metrics that can better constrain the modeled STE O3 flux in future assessments.

Statistical analysis of tropospheric ozone and its precursors using principal component analysis in an urban area of Surat, India

The objective of this study was to investigate the sources of tropospheric ozone (O3) precursors in an urban area using principal component analysis. Chemically reactive conventional pollutants such as carbon monoxide (CO), carbon dioxide (CO2), nitric oxide (NO), and nitrogen dioxide (NO2), as well as some selected meteorological parameters such as global solar radiation (SR), air temperature (AT), relative humidity (RH), wind speed (WS), and wind direction (WD), were incorporated in this analysis. Real-time observation data were obtained from two monitoring stations, Limbayat and Varachha, situated in Surat city, India. The occurrence of a peak O3 level in the summer at 5 p.m. proved the well-known fact of interconnection among the temperature, solar radiation, and increment in O3 concentration. The potencies of CO and NOwere remarkable in either the first or second principal component (PC) observed at both locations with more than 45% concentration, which alluded that the main source of O3 was urban transportation and AT contributed with 50% weightage in the PC ascertained key role of photolysis process in the O3 formation.

Monte Carlo analyses of the uncertainties in the predictions from global tropospheric ozone models: Tropospheric burdens and seasonal cycles

Abstract Because ozone is a highly reactive trace gas, estimates of its contribution to climate forcing must rely on global chemistry-transport models. These models employ many uncertain input parameters representing the sources and sinks for tropospheric ozone. Ten thousand quasi-randomly Monte Carlo sampled model runs employing a zonally-averaged global ozone model were completed and the output uncertainties were estimated in the burdens and turnovers of methane, carbon monoxide and ozone, together with the uncertainties in the ozone seasonal cycles. Multiple regression was then used to attribute the uncertainty in each output metric to each of the 183 uncertain input parameters which represented emission source sectors, chemical and photochemical rate coefficients, dry deposition velocities and biases in temperature and water vapour concentrations. We have tentatively identified sixteen chemical and photochemical rate coefficients, eight emission source sectors, ozone dry deposition and biases in temperature and water vapour as contributing most to the uncertainties in our chosen output metrics. Ten out of the sixteen chemical processes turned out to be the most important processes in the fast, photochemical balance of the troposphere. Emissions from NOx, methane, carbon monoxide and isoprene had the potential to contribute in a major way to model output uncertainties. There are, however, many limitations to our study, not the least being our use of a two-dimensional (altitude-latitude) ozone model. We have not been able to resolve the apparent conflicts between our model and the observations of ozone seasonal cycles and these must await a more rigorous treatment of tropospheric ozone sources and sinks before they can be resolved.

Modeling stratospheric intrusion and trans-Pacific transport on tropospheric ozone using hemispheric CMAQ during April 2010 - Part 1: Model evaluation and air mass characterization for stratosphere-troposphere transport.

Stratospheric intrusion and trans-Pacific transport have been recognized as a potential source of tropospheric ozone over the US. The state-of-the-science Community Multiscale Air Quality (CMAQ) modeling system has recently been extended for hemispheric-scale modeling applications (referred to as H-CMAQ). In this study, H-CMAQ is applied to study the stratospheric intrusion and trans-Pacific transport during April 2010. The results will be presented in two companion papers. In this Part 1 paper, model evaluation for tropospheric ozone (O3) is presented. Observations at the surface, by ozonesondes and airplane, and by satellite across the Northern Hemisphere are used to evaluate the model performance for O3. H-CMAQ is able to capture surface and boundary layer (defined as surface to 750hPa) O3 with a normalized mean bias (NMB) of -10%; however, a systematic underestimation with an NMB up to -30% is found in the free troposphere (defined as 750-250hPa). In addition, a new air mass characterization method is developed to distinguish influences of stratosphere-troposphere transport (STT) from the effects of photochemistry on O3 levels. This method is developed based on the ratio of O3 and an inert tracer indicating stratospheric O3 to examine the importance of photochemistry, and sequential intrusion from upper layer. During April 2010, on a monthly average basis, the relationship between surface O3 mixing ratios and estimated stratospheric air masses in the troposphere show a slight negative slope, indicating that high surface O3 values are primarily affected by other factors (i.e., emissions), whereas this relationship shows a slight positive slope at elevated sites, indicating that STT has a possible impact at elevated sites. STT shows large day-to-day variations, and STT impacts can either originate from the same air mass over the entire US with an eastward movement found during early April, or stem from different air masses at different locations indicated during late April. Based on this newly established air mass characterization technique, this study can contribute to understanding the role of STT and also the implied importance of emissions leading to high surface O3. Further research focused on emissions is discussed in a subsequent paper (Part 2).

A Stratospheric Intrusion-Influenced Ozone Pollution Episode Associated with an Intense Horizontal-Trough Event

Ozone pollution is currently a serious issue in China. As an important source of tropospheric ozone, the stratospheric ozone has received less concern. This study uses a combination of ground-based ozone measurements, the latest ERA5 reanalysis data as well as chemistry-climate model and Lagrangian Particle Dispersion Modeling (LPDM) simulations to investigate the potential impacts of stratospheric intrusion (SI) on surface ozone pollution episodes in eastern China. Station-based observations indicate that severe ozone pollution occurred from 27 April to 28 April 2018 in eastern China, with maximal values over 140 ppbv. ERA5 meteorological and ozone data suggest that a strong horizontal-trough exists at the same time, which leads to an evident SI event and brings ozone-rich air from the stratosphere to the troposphere. Using a stratospheric ozone tracer defined by NCAR’s Community Atmosphere Model with Chemistry (CAM-Chem), we conclude that this SI event contributed about 15 ppbv (15%) to the surface ozone pollution episode during 27–28 April in eastern China. The potential impacts of SI events on surface ozone variations should be therefore considered in ozone forecast and control.

Ethylene, xylene, toluene and hexane are major contributors of atmospheric ozone in Hangzhou, China, prior to the 2022 Asian Games

The occurrence of volatile organic compounds (VOCs) in the atmosphere is a major health issue, notably in China, because those compounds are the precursors of tropospheric ozone and sources of secondary organic aerosols. Also, some compounds are carcinogenic. Atmospheric nitrogen oxides (NOx) are also a source of tropospheric ozone, thus creating diseases in human respiratory systems. Therefore, controlling VOCs and NOx is essential for the welfare of local citizens and incoming 2022 Asian Games in Hangzhou. Here, we recorded daily average concentrations for 55 different VOCs species and NOx in 2017. For each VOC, we calculated the ozone formation potential, the propene equivalent concentration and the secondary organic aerosol formation potential. We used the Weather Research and Forecast coupled with Community Multi-scale Air Quality models to assess the regional transport and local sector contributions for VOCs and NOx. Results show that ethylene contributed over 16% of total ozone generated from VOCs, followed by M/P-xylene and toluene. M/P-Xylene, toluene and n-hexane were the top 3 VOCs species that generated ozone fastest. Benzene, toluene and ethylbenzene generated most secondary organic aerosols. The annual regional transport rate is 45% for VOCs and 22% for NOx. Local industry produced 28% VOCs, while local traffic contributed 64% NOx. Overall, ground-level ozone could be reduced by controlling VOCs emissions first and then controlling NOx emissions.

A deep stratosphere-to-troposphere ozone transport event over Europe simulated in CAMS global and regional forecast systems: analysis and evaluation

Abstract. Stratosphere-to-troposphere transport (STT) is an important natural source of tropospheric ozone, which can occasionally influence ground-level ozone concentrations relevant for air quality. Here, we analyse and evaluate the Copernicus Atmosphere Monitoring Service (CAMS) global and regional forecast systems during a deep STT event over Europe for the time period from 4 to 9 January 2017. The predominant synoptic condition is described by a deep upper level trough over eastern and central Europe, favouring the formation of tropopause folding events along the jet stream axis and therefore the intrusion of stratospheric ozone into the troposphere. Both global and regional CAMS forecast products reproduce the “hook-shaped” streamer of ozone-rich and dry air in the middle troposphere depicted from the observed satellite images of water vapour. The CAMS global model successfully reproduces the folding of the tropopause at various European sites, such as Trapani (Italy), where a deep folding down to 550 hPa is seen. The stratospheric ozone intrusions into the troposphere observed by WOUDC ozonesonde and IAGOS aircraft measurements are satisfactorily forecasted up to 3 days in advance by the CAMS global model in terms of both temporal and vertical features of ozone. The fractional gross error (FGE) of CAMS ozone day 1 forecast between 300 and 500 hPa is 0.13 over Prague, while over Frankfurt it is 0.04 and 0.19, highlighting the contribution of data assimilation, which in most cases improves the model performance. Finally, the meteorological and chemical forcing of CAMS global forecast system in the CAMS regional forecast systems is found to be beneficial for predicting the enhanced ozone concentrations in the middle troposphere during a deep STT event.

Future inhibition of ecosystem productivity by increasing wildfire pollution over boreal North America

Abstract. Biomass burning is an important source of tropospheric ozone (O3) and aerosols. These air pollutants can affect vegetation photosynthesis through stomatal uptake (for O3) and light scattering and absorption (for aerosols). Wildfire area burned is projected to increase significantly in boreal North America by the mid-century, while little is known about the impacts of enhanced emissions on the terrestrial carbon budget. Here, combining site-level and satellite observations and a carbon–chemistry–climate model, we estimate the impacts of fire emitted O3 and aerosols on net primary productivity (NPP) over boreal North America. Fire emissions are calculated based on an ensemble projection from 13 climate models. In the present day, wildfire enhances surface O3 by 2 ppbv (7 %) and aerosol optical depth (AOD) at 550 nm by 0.03 (26 %) in the summer. By mid-century, area burned is predicted to increase by 66 % in boreal North America, contributing more O3 (13 %) and aerosols (37 %). Fire O3 causes negligible impacts on NPP because ambient O3 concentration (with fire contributions) is below the damage threshold of 40 ppbv for 90 % summer days. Fire aerosols reduce surface solar radiation but enhance atmospheric absorption, resulting in enhanced air stability and intensified regional drought. The domain of this drying is confined to the north in the present day but extends southward by 2050 due to increased fire emissions. Consequently, wildfire aerosols enhance NPP by 72 Tg C yr−1 in the present day but decrease NPP by 118 Tg C yr−1 in the future, mainly because of the soil moisture perturbations. Our results suggest that future wildfire may accelerate boreal carbon loss, not only through direct emissions increasing from 68 Tg C yr−1 at present day to 130 Tg C yr−1 by mid-century but also through the biophysical impacts of fire aerosols.

Aviation-attributable ozone as a driver for changes in mortality related to air quality and skin cancer

Aviation is a significant source of tropospheric ozone, which is a critical UV blocking agent, an indirect precursor to the formation of particulate matter, and a respiratory health hazard. To date, investigations of human health impacts related to aviation emissions have focused on particulate matter, and no global estimate yet exists of the combined health impact of aviation due to ozone, particulate matter and UV exposure changes. We use a coupled tropospheric-stratospheric chemical-transport model with a global aviation emissions inventory to estimate the total impact of aviation on all three risk factors. We find that surface ozone due to aviation emissions is maximized during hemispheric winter due to the greater wintertime chemical lifetime of ozone, but that a smaller enhancement of 0.5 ppbv occurs during summertime. This summertime increase results in an estimated 6,800 premature mortalities per year due to ozone exposure, over three times greater than previous estimates. During the winter maximum, interaction with high background NOx concentrations results in enhanced production of nitrate aerosol and increased annual average exposure to particulate matter. This ozone perturbation is shown to be the driving mechanism behind an additional 9,200 premature mortalities due to exposure to particulate matter. However, the increase in tropospheric ozone is also found to result in 400 fewer mortalities due to melanoma skin cancer in 2006. This is the first estimate of global melanoma mortality due to aviation, and the first estimate of skin cancer mortality impacts due to aviation using a global chemical transport model.

Tropospheric ozone variations governed by changes in stratospheric circulation

The downward transport of stratospheric air can deliver significant quantities of ozone to the upper troposphere. An analysis of satellite data suggests that year-to-year variations in stratospheric circulation can account for around half of the interannual variability in tropospheric ozone levels in the northern mid-latitudes. The downward transport of stratospheric ozone is an important natural source of tropospheric ozone, particularly in the upper troposphere, where changes in ozone have their largest radiative effect1. Stratospheric circulation is projected to intensify over the coming century, which could lead to an increase in the flux of ozone from the stratosphere to the troposphere2,3,4. However, large uncertainties in the stratospheric contribution to trends and variability in tropospheric ozone levels5,6,7 make it difficult to reliably project future changes in tropospheric ozone8. Here, we use satellite measurements of stratospheric water vapour and tropospheric ozone levels collected between 2005 and 2010 to assess the effect of changes in stratospheric circulation, driven by El Nino/Southern Oscillation and the stratospheric Quasi-Biennial Oscillation, on tropospheric ozone levels. We find that interannual variations in the strength of the stratospheric circulation of around 40%—comparable to the mean change in stratospheric circulation projected this century2—lead to changes in tropospheric ozone levels in the northern mid-latitudes of around 2%, approximately half of the interannual variability. Assuming that the observed response of tropospheric ozone levels to interannual variations in circulation is a good predictor of its equilibrium response, we suggest that the projected intensification of the stratospheric circulation over the coming century could lead to small but important increases in tropospheric ozone levels.

Global ozone–CO correlations from OMI and AIRS: constraints on tropospheric ozone sources

Abstract. We present a global data set of free tropospheric ozone–CO correlations with 2° × 2.5° spatial resolution from the Ozone Monitoring Instrument (OMI) and Atmospheric Infrared Sounder (AIRS) satellite instruments for each season of 2008. OMI and AIRS have near-daily global coverage of ozone and CO respectively and observe coincident scenes with similar vertical sensitivities. The resulting ozone–CO correlations are highly statistically significant (positive or negative) in most regions of the world, and are less noisy than previous satellite-based studies that used sparser data. Comparison with ozone–CO correlations and regression slopes (dO3/dCO) from MOZAIC (Measurements of OZone, water vapour, carbon monoxide and nitrogen oxides by in-service AIrbus airCraft) aircraft profiles shows good general agreement. We interpret the observed ozone–CO correlations with the GEOS (Goddard Earth Observing System)-Chem chemical transport model to infer constraints on ozone sources. Driving GEOS-Chem with different meteorological fields generally shows consistent ozone–CO correlation patterns, except in some tropical regions where the correlations are strongly sensitive to model transport error associated with deep convection. GEOS-Chem reproduces the general structure of the observed ozone–CO correlations and regression slopes, although there are some large regional discrepancies. We examine the model sensitivity of dO3/dCO to different ozone sources (combustion, biosphere, stratosphere, and lightning NOx) by correlating the ozone change from that source to CO from the standard simulation. The model reproduces the observed positive dO3/dCO in the extratropical Northern Hemisphere in spring–summer, driven by combustion sources. Stratospheric influence there is also associated with a positive dO3/dCO because of the interweaving of stratospheric downwelling with continental outflow. The well-known ozone maximum over the tropical South Atlantic is associated with negative dO3/dCO in the observations; this feature is reproduced in GEOS-Chem and supports a dominant contribution from lightning to the ozone maximum. A major model discrepancy is found over the northeastern Pacific in summer–fall where dO3/dCO is positive in the observations but negative in the model, for all ozone sources. We suggest that this reflects a model overestimate of lightning at northern midlatitudes combined with an underestimate of the East Asian CO source.

Distribution, variability and sources of tropospheric ozone over south China in spring: Intensive ozonesonde measurements at five locations and modeling analysis

We examine the characteristics of the spatial distribution and variability of tropospheric ozone (O3) by analysis of 93 ozonesonde profiles obtained at five stations over south China (18–30°N) during a field campaign in April–May 2004. We use a global 3‐D chemical transport model (GEOS‐Chem) to interpret these characteristics and to quantify the sources of tropospheric O3 over south China during this period. The observed tropospheric O3 mixing ratios showed strong spatiotemporal variability due to a complex interplay of various dynamical and chemical processes. A prominent feature in the upper and middle troposphere (UT/MT) was the frequent occurrence of high O3mixing ratios shown as tongues extending down from the lower stratosphere or as isolated layers at all stations. The model largely captured the observed pattern of day‐to‐day variability in tropospheric O3 mixing ratios at all stations, but often underestimated those tongues or isolated layers of O3enhancements observed in the UT/MT, especially at low‐latitude stations. We found that tropospheric O3 along the southeast China coast was mainly produced within Asia. Lightning NOx emissions (over South Asia and equatorial Africa) and/or stratospheric influences were responsible for major events of high O3observed in the UT/MT at all stations. Underestimated contributions of these sources likely led to the model's underestimate in the low‐latitude UT/MT O3. This study emphasizes the need for improved understanding of lightning NOx emissions and stratospheric influences over the Eurasian and African continents and for better representation of these processes in current global models.

Tropospheric ozone production related to West African city emissions during the 2006 wet season AMMA campaign

Abstract. During African Monsoon Multidisciplinary Analyses (AMMA) airborne measurements of ozone, CO and nitrogen oxides (NOx) were collected by French and German Falcon aircraft near three cities in West Africa (Cotonou, Niamey and Ouagadougou). They have been analysed to identify the good conditions to observe ozone plumes related to city emissions during the monsoon season. Results show that an O3 increase of 40–50 ppbv above the summer average concentration took place during two specific events: one near Cotonou on the coast of the Gulf of Guinea, and the other near Niamey in the Sahel region. In both cases a high level of NOx (3–5 ppbv) is related to the ozone production. Air mass transport simulations with FLEXPART and a tracer simulation with the BOLAM mesoscale model shows that Southern Hemisphere biomass burning emissions are always at higher altitude (>3 km) compared to the city emissions. In Niamey and Ouagadougou, the daily variability of ozone and CO correlates with the FLEXPART analysis showing the role of air mass stagnation near the city for 1–2 days and advection of emissions from the vegetated areas. Absence of ozone enhancements for high CO values can be explained by the occurrence of deep convection near the city. In the Sahel region, convection must be accounted for to understand the small number of observed ozone plumes but also to explain the high level of NOx in the 3–5 ppbv range, due to increasing soil emissions after rainfall. To verify that daily ozone production can reach 20 ppbv day−1 for the NOx and CO conditions encountered near West African cities, a simulation of the CiTTyCAT Lagrangian model was conducted using the observed average chemical composition reported by other aircraft during AMMA. Such ozone production is possible for NOx levels up to 5 ppb showing that West African cities are potentially significant sources of tropospheric ozone.

Tropospheric ozone sources and wave activity over Mexico City and Houston during MILAGRO/Intercontinental Transport Experiment (INTEX-B) Ozonesonde Network Study, 2006 (IONS-06)

Abstract. During the INTEX-B (Intercontinental Chemical Transport Experiment)/ MILAGRO (Megacities Initiative: Local and Global Research Observations) experiments in March 2006 and the associated IONS-06 (INTEX Ozonesonde Network Study; http://croc.gsfc.nasa.gov/intexb/ions06.html), regular ozonesonde launches were made over 15 North American sites. The soundings were strategically positioned to study inter-regional flows and meteorological interactions with a mixture of tropospheric O3 sources: local pollution; O3 associated with convection and lightning; stratosphere-troposphere exchange. The variability of tropospheric O3 over the Mexico City Basin (MCB; 19° N, 99° W) and Houston (30° N, 95° W) is reported here. MCB and Houston profiles displayed a double tropopause in most soundings and a subtropical tropopause layer with frequent wave disturbances, identified through O3 laminae as gravity-wave induced. Ozonesondes launched over both cities in August and September 2006 (IONS-06, Phase 3) displayed a thicker tropospheric column O3 (~7 DU or 15–20%) than in March 2006; nearly all of the increase was in the free troposphere. In spring and summer, O3 laminar structure manifested mixed influences from the stratosphere, convective redistribution of O3 and precursors, and O3 from lightning NO. Stratospheric O3 origins were present in 39% (MCB) and 60% (Houston) of the summer sondes. Comparison of summer 2006 O3 structure with summer 2004 sondes (IONS-04) over Houston showed 7% less tropospheric O3 in 2006. This may reflect a sampling contrast, August to mid-September 2006 instead of July-mid August 2004.

Oceanic alkyl nitrates as a natural source of tropospheric ozone

Observations have revealed widespread emissions of alkyl nitrates from the tropical and Southern Oceans. We present the first chemical transport model simulations to examine the global impact of these emissions. Matching observed atmospheric abundances, we derive a total oceanic flux of methyl nitrate (MeONO2) and ethyl nitrate (EtONO2) equivalent to 0.35 Tg of N per year, which contributes as much as 1 DU to the tropospheric ozone column in the Western Pacific and is responsible for about 3% of the global oxidative capacity of the troposphere.

Detection of stratospheric ozone intrusions by windprofiler radars

Stratospheric ozone attenuates harmful ultraviolet radiation and protects the Earth's biosphere. Ozone is also of fundamental importance for the chemistry of the lowermost part of the atmosphere, the troposphere. At ground level, ozone is an important by-product of anthropogenic pollution, damaging forests and crops, and negatively affecting human health. Ozone is critical to the chemical and thermal balance of the troposphere because, via the formation of hydroxyl radicals, it controls the capacity of tropospheric air to oxidize and remove other pollutants. Moreover, ozone is an important greenhouse gas, particularly in the upper troposphere. Although photochemistry in the lower troposphere is the major source of tropospheric ozone, the stratosphere-troposphere transport of ozone is important to the overall climatology, budget and long-term trends of tropospheric ozone. Stratospheric intrusion events, however, are still poorly understood. Here we introduce the use of modern windprofiler radars to assist in such transport investigations. By hourly monitoring the radar-derived tropopause height in combination with a series of frequent ozonesonde balloon launches, we find numerous intrusions of ozone from the stratosphere into the troposphere in southeastern Canada. On some occasions, ozone is dispersed at altitudes of two to four kilometres, but on other occasions it reaches the ground, where it can dominate the ozone density variability. We observe rapid changes in radar tropopause height immediately preceding these intrusion events. Such changes therefore serve as a valuable diagnostic for the occurrence of ozone intrusion events. Our studies emphasize the impact that stratospheric ozone can have on tropospheric ozone, and show that windprofiler data can be used to infer the possibility of ozone intrusions, as well as better represent tropopause motions in association with stratosphere-troposphere transport.