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Insights into Tropospheric Ozone from the INTEX Ozonesonde Network Study (IONS)

Ozone profile data from soundings integrate models, aircraft and other ground-based measurements for better interpretation of atmospheric chemistry and dynamics. A well-designed network of ozonesonde stations, with consistent sampling, can answer questions not possible with short campaigns or current satellite technology. The SHADOZ (Southern Hemisphere Additional Ozonesondes) project, for example, has led to these findings about tropical ozone: definition of the zonal tropospheric wave-one pattern in equatorial ozone, characterization of the "Atlantic ozone paradox" and establishment of a link between tropical Atlantic and Indian Ocean pollution. Building on the SHADOZ concept, a short-term ozone network was formed in July-August 2004 to coordinate ozonesonde launches during the ICARTT/INTEX/NEAQS (International Consortium on Atmospheric Research on Transport and Transformation)/Intercontinental Transport Experiment/New England Air Quality Study. In IONS (INTEX Ozonesonde Network Study), more than 250 soundings, with daily frequency at half the sites, were launched from eleven North American stations and an oceanographic ship in the Gulf of Maine. Although the goal was to examine pollution influences under stable high-pressure systems and transport associated with "warm conveyor belt" flows, the INTEX study region was dominated by a series of weak frontal system that mixed aged pollution with stratospheric ozone in the middle troposphere. Deconvoluting ozone sources provides new insights into ozone in the transition between mid-latitude and polar air.

Thompson, Anne M.↗

Rapid increase in tropospheric ozone over Southeast Asia attributed to changes in precursor emission source regions and sectors

Observations indicate that tropospheric ozone (O 3 ) concentrations over Southeast Asia have been increasing rapidly since the 1990s. Here, we quantify source contributions from geographical regions and emission sectors of the two distinct types of O 3 precursors, i.e., nitrogen oxides (NO x ) and volatile organic compounds (VOCs), to the increase in tropospheric O 3 in Southeast Asia during 1990–2019 using an O 3 source tagging technique implemented in a global chemistry-climate model. In this work, the results show that although local anthropogenic emission of NO x in Southeast Asia only contributes 18% of the annual averaged near-surface O 3 concentration, the increase in local NO x emission dominates the increasing trend of O 3 concentration in Southeast Asia, accounting for 107% of the regional averaged trend of 1.07 ppb decade -1 . Increases in NO x emissions from East Asia and South Asia explain 29% of the increasing trend, but 9% is offset by the emission reduction in North America. Ground transportation is responsible for 79% of the rapid O 3 increase, followed by 39% contribution from international shipping. Because an increase in anthropogenic NO x emissions enhances the O 3 production efficiency by VOCs, the increase in near-surface O 3 concentrations in Southeast Asia is thereby largely contributed by methane and biogenic VOCs.

54 ENVIRONMENTAL SCIENCES↗

Tropospheric ozone

Photochemical equilibrium models have been used to study the effect of recent revisions in important chemical reaction rates on the calculated tropospheric ozone concentration. Reasonable agreement with observed values is obtained if the NO(x) background is approximately 0.02 to 0.03 ppb, about an order of magnitude less than used in many previous model studies, but consistent with present nitrogen budget considerations and with observations of NO2. Chemical production and loss of ozone may dominate transport terms depending on values of key chemical rate constants and of the NO(x) background. This is consistent with the structure observed in the mean annual latitudinal distribution of ozone since ozone is its own chemical precursor and regions of enhanced stratosphere-troposphere exchange are also regions of enhanced photochemical activity.

Stewart, R. W.↗

Tropospheric Ozone Over the North Pacific from Ozonesdonde Observations

As part of the TRACE-P mission, ozone vertical profile measurements were made at a number of locations in the North Pacific. At most of the sites there is also a multi-year record of ozonesonde observations. From seven locations in the western Pacific (Hong Kong; Taipei; Jeju Island, Korea; and Naha, Kagoshima, Tsukuba, and Sapporo, Japan), a site in the central Pacific (Hilo, HI), and a site on the west coast of the U.S. (Trinidad Head, CA) both a seasonal and event specific picture of tropospheric ozone over the North Pacific emerges. At all of the sites there is a pronounced spring maximum through the troposphere. There are, however, differences in the timing and strength of this feature. Over Japan the northward movement of the jet during the spring and summer influences the timing of the seasonal maximum. The ozone profiles suggest that transport of ozone rich air from the stratosphere plays a strong role in the development of this maximum. During March and April at Hong Kong ozone is enhanced in a layer that extends from the lower free troposphere into the upper troposphere that likely has its origin in biomass burning in northern Southeast Asia and equatorial Africa. During the winter the Pacific subtropical sites (latitude -25N) are dominated by air with a low-latitude, marine source that gives low ozone amounts particularly in the upper troposphere. In the summer in the boundary layer at all of the sites marine air dominates and ozone amounts are generally quite low (less than 25 ppb). The exception is near large population centers (Tokyo and Taipei but not Hong Kong) where pollution events can give amounts in excess of 80 ppb. During the TRACE-P intensive campaign period (February-April 2001) tropospheric ozone amounts were rather typical of those seen in the long-term records of the stations with multi-year soundings.

Oltmans, S. J.↗

The reservoir of ozone in the boundary layer of the eastern United States and its potential impact on the global tropospheric ozone budget

An analysis of available ozone data in the eastern two-thirds of the United States indicates that a substantial reservoir of ozone is present in the summertime. Five-year mean concentrations range from 40 to 65 ppbv. The reservoir covered an area of several million square kilometers and extends vertically from the surface to 1 to 2 km. The vertical distribution of ozone in the reservoir during midday supports a transport of additional ozone from the boundary layer to the free troposphere. Data are presented demonstrating the potential effect of transport by convective clouds and by the sea breeze circulation - mechanisms by which ozone may be transported out of the boundary layer into the free troposphere. The potential impact of this reservoir on the tropospheric ozone budget is discussed. It is shown that if less than half of the ozone mass in this reservoir is transported to the free troposphere, then the amount of ozone transported out of the boundary layer approximates the amount of ozone transported downward during a tropopause fold event.

Vukovich, F. M.↗

Arctic Tropospheric Ozone: Assessment of Current Knowledge and Model Performance

As the third most important greenhouse gas (GHG) after carbon dioxide (CO2) and methane (CH4), tropospheric ozone (O3) is also an air pollutant causing damage to human health and ecosystems. This study brings together recent research on observations and modeling of tropospheric O3 in the Arctic, a rapidly warming and sensitive environment. At different locations in the Arctic, the observed surface O3 seasonal cycles are quite different. Coastal Arctic locations, for example, have a minimum in the springtime due to O3 depletion events resulting from surface bromine chemistry. In contrast, other Arctic locations have a maximum in the spring. The 12 state-of-the-art models used in this study lack the surface halogen chemistry needed to simulate coastal Arctic surface O3 depletion in the springtime; however, the multi-model median (MMM) has accurate seasonal cycles at non-coastal Arctic locations. There is a large amount of variability among models, which has been previously reported, and we show that there continues to be no convergence among models or improved accuracy in simulating tropospheric O3 and its precursor species. The MMM underestimates Arctic surface O3 by 5 % to 15 % depending on the location. The vertical distribution of tropospheric O3 is studied from recent ozonesonde measurements and the models. The models are highly variable, simulating free-tropospheric O3 within a range of ±50 % depending on the model and the altitude. The MMM performs best, within ±8 % for most locations and seasons. However, nearly all models overestimate O3 near the tropopause (∼300 hPa or ∼8 km), likely due to ongoing issues with underestimating the altitude of the tropopause and excessive downward transport of stratospheric O3 at high latitudes. For example, the MMM is biased high by about 20 % at Eureka. Observed and simulated O3 precursors (CO, NOx, and reservoir PAN) are evaluated throughout the troposphere. Models underestimate wintertime CO everywhere, likely due to a combination of underestimating CO emissions and possibly overestimating OH. Throughout the vertical profile (compared to aircraft measurements), the MMM underestimates both CO and NOx but overestimates PAN. Perhaps as a result of competing deficiencies, the MMM O3 matches the observed O3 reasonably well. Our findings suggest that despite model updates over the last decade, model results are as highly variable as ever and have not increased in accuracy for representing Arctic tropospheric O3.

Arctic↗

NASA Satellite Measurements Show Global-scale Reductions in Free Tropospheric Ozone in 2020 and Again in 2021 During COVID-19

NASA satellite measurements show that ozone reductions throughout the Northern Hemisphere (NH) free troposphere reported for spring-summer 2020 during the Corona VIrus Disease 2019 (COVID-19) pandemic have occurred again in spring-summer 2021. The satellite measurements show that tropospheric column ozone (TCO) (mostly representative of the free troposphere) for 20oN-60oN during spring-summer for both 2020 and 2021 averaged ~3 Dobson Units (DU) (or ~7-8%) below normal. These ozone reductions in 2020 and 2021 were the lowest in the 2005- 2021 record. We also include satellite measurements of tropospheric NO2that exhibit reductions of ~10-20% in the NH in early spring-to-summer 2020 and 2021, suggesting that reduced pollution was the main cause for the low anomalies in NH TCO in 2020 and 2021. Reductions of TCO ~2DU (7 %) are also measured in the Southern Hemisphere in austral summer but are 26not associated with reduced NO2.

Tropospheric Ozone↗

Tropospheric Ozone Change from 1980 to 2010 Dominated by Equatorward Redistribution of Emissions

Ozone is an important air pollutant at the surface, and the third most important anthropogenic greenhouse gas in the troposphere. Since 1980, anthropogenic emissions of ozone precursors methane, non-methane volatile organic compounds, carbon monoxide and nitrogen oxides (NOx) have shifted from developed to developing regions. Emissions have thereby been redistributed equatorwards, where they are expected to have a stronger effect on the tropospheric ozone burden due to greater convection, reaction rates and NOx sensitivity. Here we use a global chemical transport model to simulate changes in tropospheric ozone concentrations from 1980 to 2010, and to separate the influences of changes in the spatial distribution of global anthropogenic emissions of short-lived pollutants, the magnitude of these emissions, and the global atmospheric methane concentration. We estimate that the increase in ozone burden due to the spatial distribution change slightly exceeds the combined influences of the increased emission magnitude and global methane. Emission increases in Southeast, East and South Asia may be most important for the ozone change, supported by an analysis of statistically significant increases in observed ozone above these regions. The spatial distribution of emissions dominates global tropospheric ozone, suggesting that the future ozone burden will be determined mainly by emissions from low latitudes.

Zhang, Yuqiang↗

Tropospheric Ozone Determined from Aura OMI and MLS: Evaluation of Measurements and Comparison with the Global Modeling Initiative's Chemical Transport Model

Ozone measurements from the OMI and MLS instruments on board the Aura satellite are used for deriving global distributions of tropospheric column ozone (TCO). TCO is determined using the tropospheric ozone residual method which involves subtracting measurements of MLS stratospheric column ozone (SCO) from OMI total column ozone after adjusting for intercalibration differences of the two instruments using the convective-cloud differential method. The derived TCO field, which covers one complete year of mostly continuous daily measurements from late August 2004 through August 2005, is used for studying the regional and global pollution on a timescale of a few days to months. The seasonal and zonal characteristics of the observed TCO fields are also compared with TCO fields derived from the Global Modeling Initiative's Chemical Transport Model. The model and observations show interesting similarities with respect to zonal and seasonal variations. However, there are notable differences, particularly over the vast region of the Saharan desert.

Ziemke, J. R.↗

Global atmospheric sampling program - Prospects for establishing a tropospheric ozone budget from commercial aircraft data

A preliminary analysis of zonally averaged, ozone concentration data obtained from commercial (GASP) aircraft between the equator and 60 deg North indicates that ozone in the upper troposphere exhibits a primary maximum during the spring, and, in middle latitudes, a secondary maximum in the summer of both 1975 and 1976. A late-fall/early-winter minimum also appears and seems consistent with previous upper air measurements. The April ozone maximum has been well documented and appears at the time when the stratospheric ozone content is greatest and cyclogenetic activity is most vigorous. However, the secondary maximum in June has not been widely observed or quoted as a unique feature. It is hypothesized that the rapid ascent of the tropopause between midspring and summer could account for the incorporation of ozone-rich, stratospheric air into the upper troposphere with a subsequent dilution during the following months. This may explain certain aspects of the annual ozone cycle in the lower troposphere which occasionally exhibit a bimodal distribution during the warm season.

Falconer, P. D.↗

Effects of the 2006 El Nino on Tropospheric Ozone and Carbon Monoxide: Implications for Dynamics and Biomass Burning

We have studied the effects of the 2006 El Nino on tropospheric O3 and CO at tropical and sub-tropical latitudes measured from the OMI and MLS instruments on the Aura satellite. The 2006 El Nino-induced drought allowed forest fires set to clear land to burn out of control during October and November in the Indonesian region. The effects of these fires are clearly seen in the enhancement of GO concentration measured from the MLS instrument. We have used a global model of atmospheric chemistry and transport (GMI CTM) to quantify the relative irrrportance of biomass burning and large scale transport: in producing observed changes in tropospheric O3 and CO . The model results show that during October and November both biomass burning and meteorological changes contributed almost equally to the observed increase in tropospheric O3 in the Indonesian region. The biomass component was 4-6 DU but it was limited to the Indonesian region where the fires were most intense, The dynamical component was 4-8 DU but it covered a much larger area in the Indian Ocean extending from South East Asia in the north to western Australia in the south. By December 2006, the effect of biomass taming was reduced to zero and the obsemed changes in tropospheric O3 were mostly due to dynamical effects. The model results show an increase of 2-3% in the global burden of tropospheric ozone. In comparison, the global burdean of CO increased by 8-12%.

Chandra, S.↗

Tropospheric Ozone Climatology over Irene, South Africa, From 1990-1994 and 1998-2002

This paper describes ozone profiles from sonde data during the period of NASA s TRACE-A and the more recent SHADOZ (Southern Hemisphere Additional Ozonesondes) period. The data were taken by the South African Weather Service at the Irene (25 deg.54 min S; 28 deg. 13 min. E) station near Pretoria, South Africa, an area that is a unique mixture of local industry, heavy biofuels use and importation of biomass burning ozone from neighboring countries to the north. The main findings are: (1) With its geographical position at the edge of the subtropical transition zone, mid- latitude dynamical influences are evident at Irene, predominantly in winter when upper tropospheric ozone is enhanced as a result of stratospheric-tropospheric exchange. (2) There has been an increase in the near-surface ozone amount between the early 1990s and a decade later, presumably due to an influx of rural population toward the Johannesburg-Pretoria area, as well as with industrial growth and development. (3) Most significant for developing approaches for satellite ozone profile climatologies, cluster analysis has enabled the delineation of a background and "most polluted" profile. Enhancements of at least 30% occur throughout the troposphere in spring and in certain layers increases of 100 % are observed.

Diab, R. D.↗

Arctic tropospheric ozone: assessment of current knowledge and model performance

As the third most important greenhouse gas (GHG) after carbon dioxide (CO 2 ) and methane (CH 4 ), tropospheric ozone (O 3 ) is also an air pollutant causing damage to human health and ecosystems. This study brings together recent research on observations and modeling of tropospheric O 3 in the Arctic, a rapidly warming and sensitive environment. At different locations in the Arctic, the observed surface O 3 seasonal cycles are quite different. Coastal Arctic locations, for example, have a minimum in the springtime due to O 3 depletion events resulting from surface bromine chemistry. In contrast, other Arctic locations have a maximum in the spring. The 12 state-of-the-art models used in this study lack the surface halogen chemistry needed to simulate coastal Arctic surface O 3 depletion in the springtime; however, the multi-model median (MMM) has accurate seasonal cycles at non-coastal Arctic locations. There is a large amount of variability among models, which has been previously reported, and we show that there continues to be no convergence among models or improved accuracy in simulating tropospheric O 3 and its precursor species. The MMM underestimates Arctic surface O 3 by 5% to 15% depending on the location. The vertical distribution of tropospheric O 3 is studied from recent ozonesonde measurements and the models. The models are highly variable, simulating free-tropospheric O 3 within a range of ±50% depending on the model and the altitude. The MMM performs best, within ±8% for most locations and seasons. However, nearly all models overestimate O 3 near the tropopause (~300 hPa or ~8 km), likely due to ongoing issues with underestimating the altitude of the tropopause and excessive downward transport of stratospheric O 3 at high latitudes. For example, the MMM is biased high by about 20% at Eureka. Observed and simulated O 3 precursors (CO, NO x , and reservoir PAN) are evaluated throughout the troposphere. Models underestimate wintertime CO everywhere, likely due to a combination of underestimating CO emissions and possibly overestimating OH. Throughout the vertical profile (compared to aircraft measurements), the MMM underestimates both CO and NO x but overestimates PAN. Perhaps as a result of competing deficiencies, the MMM O 3 matches the observed O 3 reasonably well. Our findings suggest that despite model updates over the last decade, model results are as highly variable as ever and have not increased in accuracy for representing Arctic tropospheric O 3 .

54 ENVIRONMENTAL SCIENCES↗

Satellite Remote-Sensing Capability to Assess Tropospheric-Column Ratios of Formaldehyde and Nitrogen Dioxide: Case Study During the Long Island Sound Tropospheric Ozone Study 2018 (LISTOS 2018) Field Campaign

Satellite retrievals of tropospheric-column formaldehyde (HCHO) and nitrogen dioxide (NO 2 ) are frequently used to investigate the sensitivity of ozone (O 3 ) production to emissions of nitrogen oxides and volatile organic carbon compounds. This study inter-compared the systematic biases and uncertainties in retrievals of NO 2 and HCHO, as well as resulting HCHO–NO 2 ratios (FNRs), from two commonly applied satellite sensors to investigate O 3 production sensitivities (Ozone Monitoring Instrument, OMI, and TROPOspheric Monitoring Instrument, TROPOMI) using airborne remote-sensing data taken during the Long Island Sound Tropospheric Ozone Study 2018 between 25 June and 6 September 2018. Compared to aircraft-based HCHO and NO 2 observations, the accuracy of OMI and TROPOMI were magnitude-dependent with high biases in clean environments and a tendency towards more accurate comparisons to even low biases in moderately polluted to polluted regions. OMI and TROPOMI NO 2 systematic biases were similar in magnitude (normalized median bias, NMB = 5 %–6 %; linear regression slope ≈ 0.5–0.6), with OMI having a high median bias and TROPOMI resulting in small low biases. Campaign-averaged uncertainties in the three satellite retrievals (NASA OMI; Quality Assurance for Essential Climate Variables, QA4ECV OMI; and TROPOMI) of NO 2 were generally similar, with TROPOMI retrievals having slightly less spread in the data compared to OMI. The three satellite products differed more when evaluating HCHO retrievals. Campaign-averaged tropospheric HCHO retrievals all had linear regression slopes ∼0.5 and NMBs of 39 %, 17 %, 13 %, and 23 % for NASA OMI, QA4ECV OMI, and TROPOMI at finer (0.05° x 0.05°) and coarser (0.15° x 0.15°) spatial resolution, respectively. Campaign-averaged uncertainty values (root mean square error, RMSE) in NASA and QA4ECV OMI HCHO retrievals were ~9.0 x 10 15 molecules cm –2 (∼ 50 %–55 % of mean column abundance), and the higher-spatial-resolution retrievals from TROPOMI resulted in RMSE values ∼30 % lower. Spatially averaging TROPOMI tropospheric-column HCHO, along with NO 2 and FNRs, to resolutions similar to the OMI reduced the uncertainty in these retrievals. Systematic biases in OMI and TROPOMI NO 2 and HCHO retrievals tended to cancel out, resulting in all three satellite products comparing well to observed FNRs. However, while satellite-derived FNRs had minimal campaign-averaged median biases, unresolved errors in the indicator species did not cancel out in FNR calculations, resulting in large RMSE values compared to observations. Uncertainties in HCHO retrievals were determined to drive the unresolved biases in FNR retrievals.

Matthew S. Johnson↗

Remote measurement of tropospheric ozone

It is shown that a differential absorption lidar employing a pulsed CO2 laser and a direct detection receiver is capable of significantly improving the existing data base on the tropospheric ozone burden. As a ground-based system, the lidar could obtain urban to regional scale O3 measurements with a vertical or horizontal resolution of at least 1 km in the troposphere. As a space-based system, it could obtain global scale coverage of the O3 burden below the stratospheric maximum of O3.

Bufton, J. L.↗

Processes Affecting Tropospheric Ozone over Africa

This is a Workshop Report prepared for Eos, the weekly AGU magazine, The workshop took place between 26-28 January 2004 at the University of KwaZulu-Natal in Durban, South Africa and was attended by 26 participants (http//www.geography.und.ac.za). Considerable progress has been made in ozone observations except for northern Africa (large data gaps) and west Africa (to be covered by the French-sponsored AMMA program). The present-day ozone findings were evaluated and reviewed by speakers using Aircraft data (MOZAIC program), NASA satellites (MOPITT, TRMM, TOMS) and ozone soundings (SHADOZ). Besides some ozone gaps, there are challenges posed by the need to assess the relative strengths of photochemical and dynamic influences on the tropospheric ozone budget. Biogenic, biofuels, biomass burning sources of ozone precursors remain highly uncertain. Recent findings (by NASA's Chatfield and Thompson, using satellite and sounding data) show significant impact of Indian Ocean pollution on African ozone. European research on pollutants over the Mediterranean and the middle east, that suggests that ozone may be exported to Africa from these areas, also needs to be considered.

Diab, Roseanne D.↗

The Response of Tropospheric Ozone to ENSO in Observations and a Chemistry-Climate Simulation

The El Nino-Southern Oscillation (ENSO) is the dominant mode of tropical variability on interannual time scales. ENSO appears to extend its influence into the chemical composition of the tropical troposphere. Recent results have revealed an ENSO induced wave-l anomaly in observed tropical tropospheric column ozone. This results in a dipole over the western and eastern tropical Pacific, whereby differencing the two regions produces an ozone anomaly with an extremely high correlation to the Nino 3.4 Index. We have successfully reproduced this result using the Goddard Earth Observing System Version 5 (GEOS-5) general circulation model coupled to a comprehensive stratospheric and tropospheric chemical mechanism forced with observed sea surface temperatures over the past 25 years. An examination of the modeled ozone field reveals the vertical contributions of tropospheric ozone to the column over the western and eastern Pacific region. We will show targeted comparisons with observations from NASA's Aura satellite Microwave Limb Sounder (MLS), and the Tropospheric Emissions Spectrometer (TES) to provide insight into the vertical structure of ozone changes. The tropospheric ozone response to ENSO could be a useful chemistry-climate model evaluation tool and should be considered in future modeling assessments.

Oman, L. D.↗

Modeling and Observations of the Response of Tropical Tropospheric Ozone to ENSO

The El Nino-Southern Oscillation (ENSO) is the dominant mode of tropical variability on interannual time scales. ENSO appears to extend its influence into the chemical composition of the tropical troposphere, Recent results have revealed an ENSO induced wave-1 anomaly in observed tropical tropospheric column ozone, This results in a dipole over the western and eastern tropical Pacific, whereby differencing the two regions produces an ozone anomaly with an extremely high correlation to the Nino 3.4 Index. We have successfully reproduced this result using the Goddard Earth Observing System Version 5 (GEOS-5) general circulation model coupled to a comprehensive stratospheric and tropospheric chemical mechanism forced with observed sea surface temperatures over the past 25 years, An examination of the modeled ozone field reveals the vertical contributions of tropospheric ozone to the column over the western and eastern Pacific region, We will show targeted comparisons with SHADOZ ozonesondes over these regions to provide insight into the vertical structure. Also, comparisons with NASA's Aura satellite Microwave Limb Sounder (MLS) and Tropospheric Emissions Spectrometer (TES) instruments and other appropriate data sets will be shown. In addition, the water vapor response to ENSO will be compared to help illuminate its role relative to dynamics in impacting ozone concentrations. These results indicate that the tropospheric ozone response to ENSO is potentially a very useful chemistry-climate diagnostic and should be considered in future modeling assessments.

Oman, L. D.↗