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Urban and Rural Ozone Collect over Lusaka (Zambia, 15.5 S, 28 E) during SAFARI-2000 (September 2000)

In early September, throughout south central Africa, seasonal clearing of dry vegetation and the production of charcoal for cooking leads to intense smoke haze and ozone formation. Ozone soundings made over Lusaka in early September 2000 recorded layers of high ozone (greater than 125 ppbv at 5 km) during two stagnant periods, broken by a frontal passage that reduced boundary layer ozone by 30%. During the 6-day measurement period, surface ozone concentrations ranged from 50-95 ppbv and integrated tropospheric ozone from the soundings was 39-54 Dobson Units (note 1.3 km elevation at the launch site). A stable layer of high ozone at 2-5 km was advected from rural burning regions in western Zambia and neighboring countries, making Lusaka a collection point for transboundary pollution. This is confirmed by trajectories that show ozone leaving Angola, Namibia, Botswana and South Africa before heading toward the Indian Ocean and returning to Lusaka via Mozambique and Zimbabwe. Ozone in the mixed layer at Lusaka is heavily influenced by local sources.

Thompson, Anne M.↗

Machine learning-based bias-corrected future projections of ozone concentrations from a chemistry-climate model

Reliable projection of future near-surface ozone is crucial for air quality management and health risk assessment. However, potential biases in spatial distribution, magnitude and trends in ozone concentrations simulated by global chemistry-climate models limit their applicability in regional-scale evaluations. In this study, LightGBM, a machine learning (ML) algorithm is applied to correct biases in CESM2-simulated ozone concentrations over China, the United States and Europe and calibrate future ozone projections under two diverse Shared Socioeconomic Pathways (SSP1-2.6 and SSP5-8.5) scenarios from 2020 to 2060. The ML-based correction significantly improves the spatial distribution and reduces the model bias by 40%–60%. It also reverses the potentially incorrect trend of ozone change under SSP1-2.6 in eastern China. When applying ML-based bias correction to CESM2 future projections, warm season mean ozone concentrations decrease across China, the United States, and Europe by –13.5, –17.9, and –13.7 µg/m³, respectively, between 2020 and 2060 in SSP1-2.6, while they increase by 9.4, 2.0, and 5.2 µg/m³ in SSP5-8.5. Decomposition analysis show that changes in anthropogenic emissions dominate future ozone changes in both scenarios, while strong climate penalty from ozone changes occurs in polluted eastern China and climate benefit is found in western China, the United States and Europe under SSP5-8.5. These findings demonstrate the value of combining ML with chemistry-climate models to produce more accurate air quality projections, thereby informing more effective and region-specific environmental protection strategies.

Chemistry Model↗

Summertime ozone pollution in China affected by stratospheric quasi-biennial oscillation

In recent years, the near-surface ozone (O 3 ) level has been rising fast in China, with increasing damage to human health and ecosystems. In this study, the impact of stratospheric quasi-biennial oscillation (QBO) on interannual variations in summertime tropospheric O 3 over China is investigated based on GEOS-Chem model simulations and satellite retrievals. QBO has a significant positive correlation with near-surface O 3 concentrations over central China (92.5–112.5° E, 26–38° N) when the sea surface temperature (SST) over the eastern tropical Pacific is warmer than normal, with a correlation coefficient of 0.53, but QBO has no significant effect on O 3 under the cold SST anomaly. Compared to the easterly phase of QBO, the near-surface O 3 concentrations have an increase of up to 3 ppb (5% relative to the average) over central China during its westerly phase under the warm SST anomaly. O 3 also increases above the surface and up to the upper troposphere, with a maximum increase of 2–3 ppb (3%–5%) in 850–500 hPa over central China when comparing westerly phase to easterly phase. Process-based analysis and sensitivity simulations suggest that the O 3 increase over central China is mainly attributed to the anomalous downward transport of O 3 during the westerly phase of QBO when a warm SST anomaly occurs in the eastern tropical Pacific, while the local chemical reactions and horizontal transport processes partly offset the O 3 increase. This work suggests a potentially important role of QBO and the related vertical transport process in affecting near-surface O 3 air quality, with an indication for O 3 pollution prediction and prevention.

54 ENVIRONMENTAL SCIENCES↗

Urban and Rural Ozone Pollution Over Lusaka (Zambia, 15.5S, 25E) During SAFARI-2000 (September 2000)

In early September, throughout south central Africa, seasonal clearing of dry vegetation and the production of charcoal for cooking leads to intense smoke haze and ozone formation. Ozone soundings made over Lusaka during a six-day period in early September 2000 recorded layers of high ozone (greater than 125 ppbv at 5 km) during two stagnant periods, interspersed by a frontal passage that reduced boundary layer ozone by 30 percent. Smoke aerosol column variations aloft and total ozone were monitored by a sun photometer. During the 6-day measurement period, surface ozone concentrations ranged from 50-95 ppbv and integrated tropospheric ozone from the soundings was 39- 54 Dobson Units (note 1.3 km elevation at the launch site). High ozone concentrations above the mixed and inversion layers were advected from rural burning regions in western Zambia where SAFARI aircraft and ground-based instruments observed intense biomass fires and elevated aerosol and trace gas amounts. TOMS tropospheric ozone and smoke aerosols products show the distribution of biomass burning and associated pollution throughout southern Africa in September 2000. Animations of satellite images and trajectories confirm pollutant recirculation over south central African fires, exit of ozone from Mozambique and Tanzania to the Indian Ocean and the characteristic buildup of tropospheric ozone over the Atlantic from western African outflow.

Thompson, Anne M.↗

Lightning NOx and Impacts on Air Quality

Lightning generates relatively large but uncertain quantities of nitrogen oxides, critical precursors for ozone and hydroxyl radical (OH), the primary tropospheric oxidants. Lightning nitrogen oxide strongly influences background ozone and OH due to high ozone production efficiencies in the free troposphere, effecting small but non-negligible contributions to surface pollutant concentrations. Lightning globally contributes 3-4 ppbv of simulated annual-mean policy-relevant background (PRB) surface ozone, comprised of local, regional, and hemispheric components, and up to 18 ppbv during individual events. Feedbacks via methane may counter some of these effects on decadal time scales. Lightning contributes approximately 1 percent to annual-mean surface particulate matter, as a direct precursor and by promoting faster oxidation of other precursors. Lightning also ignites wildfires and contributes to nitrogen deposition. Urban pollution influences lightning itself, with implications for regional lightning-nitrogen oxide production and feedbacks on downwind surface pollution. How lightning emissions will change in a warming world remains uncertain.

Reactive nitrogen oxides↗

Multidecadal Trends in Ozone Chemistry in the Baltimore-Washington Region

Over the past four decades, policy-led reductions in anthropogenic emissions have improved air quality over the Baltimore-Washington region (BWR). Most of the improvements in meeting the ozone air quality metrics (NAAQS) did not occur until the early 2000s despite large reductions in ozone precursors (NOx, CO, and volatile organic compounds (VOCs)) in the prior decades. We use observations of ozone and ozone precursors from satellites, ground-based sites, and the 2011 DISCOVER-AQ aircraft campaign in Maryland to illustrate how ozone chemistry in the BWR evolved between 1972 and 2019. Analysis of weekday vs weekend probability of ozone exceedance indicates the BWR transitioned to the NOx-limited regime by 2000–2003. A data-constrained box model agrees with this transition period and illustrates the key roles of reduced emissions of formaldehyde (HCHO), aromatics, and other VOCs since 1996, which reduced the peak of ozone production at the time of the transition and likely prevented the BWR from experiencing worsening surface air quality as the region transitioned to NOx-limited chemistry. Analysis of satellite observations of tropospheric column HCHO to NO2 analyzed using a new approach for evaluation of chemical regimes derived from DISCOVER-AQ data also provide a consistent depiction of the timing of the transition period that we infer from ground-based observations and the box model. Finally, despite significant improvements in air quality over the past two decades, the BWR still has not met the EPA standard for surface ozone. With predominantly NOx-limited ozone chemistry over the BWR, continued decreases in emission of NOx will slow the rate of ozone production and help improve air quality. We highlight emissions of NO2 from the diesel truck fleet as a worthwhile focus for future policy because emissions from this source appear to influence day-of-week variations in observed NO2, with an accompanying effect on ozone.

Ozone↗

Ozone, Tropospheric

In the early part of the 20th century, ground-based and balloon-borne measurements discovered that most of atmosphere's ozone is located in the stratosphere with highest concentrations located between 15 and 30 km (9,3 and 18.6 miles). For a long time, it was believed that tropospheric ozone originated from the stratosphere and that most of it was destroyed by contact with the earth's surface. Ozone, O3, was known to be produced by the photo-dissociation of molecular oxygen, O2, a process that can only occur at wavelengths shorter than 242 nm. Because such short-wave-length radiation is present only in the stratosphere, no tropospheric ozone production is possible by this mechanism. In the 1940s, however, it became obvious that production of ozone was also taking place in the troposphere. The overall reaction mechanism was eventually identified by Arie Haagen-Smit of the California Institute of Technology, in highly polluted southern California. The copious emissions from the numerous cars driven there as a result of the mass migration to Los Angeles after World War 2 created the new unpleasant phenomenon of photochemical smog, the primary component of which is ozone. These high levels of ozone were injuring vegetable crops, causing women's nylons to run, and generating increasing respiratory and eye-irritation problems for the populace. Our knowledge of tropospheric ozone increased dramatically in the early 1950s as monitoring stations and search centers were established throughout southern California to see what could be done to combat this threat to human health and the environment.

Fishman, Jack↗

Dynamical response of the tropical total ozone to sea surface temperature changes

Interannual variations of total ozone in the equatorial region are discussed in terms of the lower-stratospheric dynamical processes associated with sea surface temperature (SST) changes on an El Nino-Southern Oscillation time scale. Tropospheric diabatic heating by the latent heat release in convective systems drives the interannual variations of tropopause height and atmospheric vertical motions. The adiabatic cooling associated with the dynamically forced ascending motion is subject to radiative heating, which further extends the upwelling motion into the stratosphere. SST variations can thus influence total ozone amounts by changing the tropopause height and vertical advection through modulation of tropospheric diabatic heating. Mechanistic relationships that describe total ozone fluctuations through the advection effect and the tropopause effect of SST variations are derived using the equivalent potential temperature. Total ozone fluctuations are estimated using a quantitative formulation of these mechanistic equations together with the observed SST data. These results indicate that the interannual variations of the zonal wave component of equatorial total ozone are governed by the tropopause effect of SST variations. Preliminary investigation suggests that the annual cycle of tropical total ozone is coupled to the tropopause height changes under the influence of the planetary wave-induced lower-stratospheric temperature rather than local SST.

Hasebe, Fumio↗

Impact of Transpacific Aerosol on Air Quality over the United States: A Perspective from Aerosol-Cloud-Radiation Interactions

Observations have well established that aerosols from various sources in Asia, Europe, and Africa can travel across the Pacific and reach the contiguous United States (U.S.) at least on episodic bases throughout a year, with a maximum import in spring. The imported aerosol not only can serve as an additional source to regional air pollution (e.g., direct input), but also can influence regional air quality through the aerosol-cloud-radiation (ACR) interactions that change local and regional meteorology. This study assessed impacts of the transpacific aerosol on air quality, focusing on surface ozone and PM2.5, over the U.S. using the NASA Unified Weather Research Forecast model. Based on the results of 3- month (April to June of 2010) simulations, the impact of direct input (as an additional source) of transpacific aerosol caused an increase of surface PM2.5 concentration by approximately 1.5 micro-g/cu m over the west coast and about 0.5 micro-g/cu m over the east coast of the U.S. By influencing key meteorological processes through the ACR interactions, the transpacific aerosol exerted a significant effect on both surface PM2.5 (+/-6 micro-g/cu m3) and ozone (+/-12 ppbv) over the central and eastern U.S. This suggests that the transpacific transport of aerosol could either improve or deteriorate local air quality and complicate local effort toward the compliance with the U.S. National Ambient Air Quality Standards.

Tao, Zhining↗

The Influence of European Pollution on Ozone in the Near East and Northern Africa

We present a modeling study of the long-range transport of pollution from Europe, showing that European emissions regularly elevate surface ozone by as much as 20 ppbv in summer in northern Africa and the Near East. European emissions cause 50-150 additional violations per year (i.e. above those that would occur without European pollution) of the European health standard for ozone (8-h average greater than 120 micrograms per cubic meters or approximately 60 ppbv) in northern Africa and the Near East. We estimate that European ozone pollution is responsible for 50 000 premature mortalities globally each year, of which the majority occurs outside of Europe itself, including 37% (19 000) in northern Africa and the Near East. Much of the pollution from Europe is exported southward at low altitudes in summer to the Mediterranean Sea, northern Africa and the Near East, regions with favorable photochemical environments for ozone production. Our results suggest that assessments of the human health benefits of reducing ozone precursor emissions in Europe should include effects outside of Europe, and that comprehensive planning to improve air quality in northern Africa and the Near East likely needs to address European emissions.

Duncan, B. N.↗

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.↗

Long-term trends of impacts of global gasoline and diesel emissions on ambient PM 2.5 and O 3 pollution and the related health burden for 2000–2015

Global economic development and urbanization during the past two decades have driven the increases in demand of personal and commercial vehicle fleets, especially in developing countries, which has likely resulted in changes in year-to-year vehicle tailpipe emissions associated with aerosols and trace gases. However, long-term trends of impacts of global gasoline and diesel emissions on air quality and human health are not clear. In this study, we employ the Community Earth System Model in conjunction with the newly developed Community Emissions Data System as anthropogenic emission inventory to quantify the long-term trends of impacts of global gasoline and diesel emissions on ambient air quality and human health for the period of 2000–2015. Global gasoline and diesel emissions contributed to regional increases in annual mean surface PM 2.5 (particulate matter with aerodynamic diameters ≤2.5 μm) concentrations by up to 17.5 and 13.7 µg m –3 , and surface ozone (O 3 ) concentrations by up to 7.1 and 7.2 ppbv, respectively, for 2000–2015. However, we also found substantial declines of surface PM 2.5 and O 3 concentrations over Europe, the US, Canada, and China for the same period, which suggested the co-benefits of air quality and human health from improving gasoline and diesel fuel quality and tightening vehicle emissions standards. Globally, we estimate the mean annual total PM 2.5- and O 3 -induced premature deaths are 139 700–170 700 for gasoline and 205 200–309 300 for diesel, with the corresponding years of life lost of 2.74–3.47 and 4.56–6.52 million years, respectively. Diesel and gasoline emissions create health-effect disparities between the developed and developing countries, which are likely to aggravate afterwards.

54 ENVIRONMENTAL SCIENCES↗

On detecting a trend in the residual circulation from observations of column HCl

The troposphere is the part of the atmosphere where people live. The troposphere goes up to about 12 km above the earth over places at middle latitudes like Washington, D.C. The next layer of air up in the atmosphere is called the stratosphere. The tropopause separates the troposphere and stratosphere. Most of the ozone in the atmosphere is in the stratosphere where it protects people from the harmful rays in sunlight. Near the earth s surface, ozone is a pollutant. In general, air travels from the troposphere to the stratosphere through upward motion in the tropics. Most of the air comes back down to the troposphere at middle latitudes. The so-called "stratospheric residual circulation" moves the air in the stratosphere from the tropics to the middle latitudes. In this way, the amount of air that moves out of the stratosphere into the troposphere at middle latitudes depends on the strength of the residual circulation. This overturning of the atmosphere is important as it brings chemicals produced by the activities of people into the stratosphere. Most notable are chlorofluorocarbons (CFCs) that destroy stratospheric ozone. The transport of air out of the stratosphere removes ozone-destroying chemicals, but also brings ozone into the troposphere.

Olsen, M. A.↗

Airborne lidar mapping of vertical ozone distributions in support of the 1990 Clean Air Act Amendments

The 1990 Clean Air Act Amendments mandated attainment of the ozone standard established by the U.S. Environmental Protection Agency. Improved photochemical models validated by experimental data are needed to develop strategies for reducing near surface ozone concentrations downwind of urban and industrial centers. For more than 10 years, lidar has been used on large aircraft to provide unique information on ozone distributions in the atmosphere. However, compact airborne lidar systems are needed for operation on small aircraft of the type typically used on regional air quality investigations to collect data with which to develop and validate air quality models. Data presented in this paper will consist of a comparison between airborne differential absorption lidar (DIAL) and airborne in-situ ozone measurements. Also discussed are future plans to improve the airborne ultraviolet-DIAL for ozone and other gas observations and addition of a Fourier Transform Infrared (FTIR) emission spectrometer to investigate the effects of other gas species on vertical ozone distribution.

Uthe, Edward E.↗

Global Distribution and Trends of Tropospheric Ozone: An Observation-Based Review

Tropospheric ozone plays a major role in Earth's atmospheric chemistry processes and also acts as an air pollutant and greenhouse gas. Due to its short lifetime, and dependence on sunlight and precursor emissions from natural and anthropogenic sources, tropospheric ozone's abundance is highly variable in space and time on seasonal, interannual and decadal time-scales. Recent, and sometimes rapid, changes in observed ozone mixing ratios and ozone precursor emissions inspired us to produce this up-to-date overview of tropospheric ozone's global distribution and trends. Much of the text is a synthesis of in situ and remotely sensed ozone observations reported in the peer-reviewed literature, but we also include some new and extended analyses using well-known and referenced datasets to draw connections between ozone trends and distributions in different regions of the world. In addition, we provide a brief evaluation of the accuracy of rural or remote surface ozone trends calculated by three state-of-the-science chemistry-climate models, the tools used by scientists to fill the gaps in our knowledge of global tropospheric ozone distribution and trends.

Mixing ratios↗

Characterization of Errors in Satellite-Based HCHO/NO 2 Tropospheric Column Ratios With Respect to Chemistry, Column-to-PBL Translation, Spatial Representation, and Retrieval Uncertainties

The availability of formaldehyde (HCHO) (a proxy for volatile organic compound reactivity) and nitrogen dioxide (NO 2 ) (a proxy for nitrogen oxides) tropospheric columns from ultraviolet–visible (UV–Vis) satellites has motivated many to use their ratios to gain some insights into the near-surface ozone sensitivity. Strong emphasis has been placed on the challenges that come with transforming what is being observed in the tropospheric column to what is actually in the planetary boundary layer (PBL) and near the surface; however, little attention has been paid to other sources of error such as chemistry, spatial representation, and retrieval uncertainties. Here we leverage a wide spectrum of tools and data to quantify those errors carefully. Concerning the chemistry error, a well-characterized box model constrained by more than 500 h of aircraft data from NASA's air quality campaigns is used to simulate the ratio of the chemical loss of HO 2 + RO 2 (LRO x ) to the chemical loss of NO x (LNO x ). Subsequently, we challenge the predictive power of HCHO/NO 2 ratios (FNRs), which are commonly applied in current research, in detecting the underlying ozone regimes by comparing them to LRO x /LNO x . FNRs show a strongly linear (R 2 =0.94) relationship with LRO x /LNO x , but only on the logarithmic scale. Following the baseline (i.e., ln(LRO x /LNO x ) = −1.0 ± 0.2) with the model and mechanism (CB06, r2) used for segregating NO x -sensitive from VOC-sensitive regimes, we observe a broad range of FNR thresholds ranging from 1 to 4. The transitioning ratios strictly follow a Gaussian distribution with a mean and standard deviation of 1.8 and 0.4, respectively. This implies that the FNR has an inherent 20 % standard error (1σ) resulting from not accurately describing the RO x –HO x cycle. We calculate high ozone production rates (PO 3 ) dominated by large HCHO × NO 2 concentration levels, a new proxy for the abundance of ozone precursors. The relationship between PO 3 and HCHO × NO 2 becomes more pronounced when moving towards NO x -sensitive regions due to nonlinear chemistry; our results indicate that there is fruitful information in the HCHO × NO 2 metric that has not been utilized in ozone studies. The vast amount of vertical information on HCHO and NO 2 concentrations from the air quality campaigns enables us to parameterize the vertical shapes of FNRs using a second-order rational function permitting an analytical solution for an altitude adjustment factor to partition the tropospheric columns into the PBL region. We propose a mathematical solution to the spatial representation error based on modeling isotropic semivariograms. Based on summertime-averaged data, the Ozone Monitoring Instrument (OMI) loses 12 % of its spatial information at its native resolution with respect to a high-resolution sensor like the TROPOspheric Monitoring Instrument (TROPOMI) (> 5.5 × 3.5 km 2 ). A pixel with a grid size of 216 km 2 fails at capturing ∼ 65 % of the spatial information in FNRs at a 50 km length scale comparable to the size of a large urban center (e.g., Los Angeles). We ultimately leverage a large suite of in situ and ground-based remote sensing measurements to draw the error distributions of daily TROPOMI and OMI tropospheric NO 2 and HCHO columns. At a 68 % confidence interval (1σ), errors pertaining to daily TROPOMI observations, either HCHO or tropospheric NO 2 columns, should be above 1.2–1.5 × 10 16 molec. cm −2 to attain a 20 %–30 % standard error in the ratio. This level of error is almost non-achievable with the OMI given its large error in HCHO. The satellite column retrieval error is the largest contributor to the total error (40 %–90 %) in the FNRs. Due to a stronger signal in cities, the total relative error (< 50 %) tends to be mild, whereas areas with low vegetation and anthropogenic sources (e.g., the Rocky Mountains) are markedly uncertain (> 100 %). Our study suggests that continuing development in the retrieval algorithm and sensor design and calibration is essential to be able to advance the application of FNRs beyond a qualitative metric.

Amir H. Souri↗

Asian Outflow and Trans-Pacific Transport of Carbon Monoxide and Ozone Pollution: An Integrated Satellite, Aircraft, and Model Perspective

Satellite observations of carbon monoxide (CO) from the Measurements of Pollution in the Troposphere (MOPITT) instrument are combined with measurements from the Transport and Chemical Evolution Over the Pacific (TRACE-P) aircraft mission over the northwest Pacific and with a global three-dimensional chemical transport model (GEOS-CHEM) to quantify Asian pollution outflow and its trans-Pacific transport during spring 2001. Global CO column distributions in MOPITT and GEOS-CHEM are highly correlated (R(exp 2) = 0.87), with no significant model bias. The largest regional bias is over Southeast Asia, where the model is 18% too high. A 60% decrease of regional biomass burning emissions in the model (to 39 Tg/yr) would correct the discrepancy; this result is consistent with TRACE-P observations. MOPITT and TRACE-P also give consistent constraints on the Chinese source of CO from fuel combustion (181 Tg CO/yr). Four major events of trans-Pacific transport of Asian pollution in spring 2001 were seen by MOPITT, in situ platforms, and GEOS-CHEM. One of them was sampled by TRACE-P (26-27 February) as a succession of pollution layers over the northeast Pacific. These layers all originated from one single event of Asian outflow that split into northern and southern plumes over the central Pacific. The northern plume (sampled at 6-8 km off California) had no ozone enhancement. The southern subsiding plume (sampled at 2-4 km west of Hawaii) contained a 8 - 17 ppbv ozone enhancement, driven by decomposition of peroxyacetylnitrate (PAN) to nitrogen oxides (NOx). This result suggests that PAN decomposition in trans-Pacific pollution plumes subsiding over the United States could lead to significant enhancements of surface ozone.

Heald, Colette L.↗