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Atmospheric Trace Gas (NO2 and Ozone) Dynamics over Coastal Waters near Polluted Urban Regions

At the interface between the land, oceans, and atmosphere, coastal regions are highly dynamic environments, characterized by strong variability in both water and air quality. Variability in atmospheric composition is associated with highly variable anthropogenic emissions, as well as complex meteorological processes that influence the circulation and accumulation of atmospheric pollutants at the land-ocean interface. Assessing the spatial and temporal dynamics of atmospheric pollutants, aerosols, and absorbing trace gases in coastal areas is critical for improving modeling of coastal tropospheric air quality, developing accurate satellite retrievals of coastal ocean color and biological processes, determining impacts of atmospheric pollution on human health, and assessing the ecological implications of atmospheric pollutant deposition for coastal terrestrial and aquatic ecosystems.Here, we present new measurements of atmospheric trace gas (NO2, and ozone) dynamics across a range of estuarine and coastal waters near urban regions. Measurements were conducted from research vessels using NASA's shipboard Pandora spectrometers, as part of recent multidisciplinary, multiplatform field campaigns, including the 2016 KORUS OC/AQ field campaign in the Yellow Sea and East Sea/Sea of Japan, the 2017/2018 OLWETS field campaign in the Chesapeake Bay estuary, and the 2018 LISTOS field campaign in the Long Island Sound. Shipboard measurements over these coastal waters were integrated with measurements from a ground-based Pandora network to examine differences in air quality over the land and over the ocean. Measurements were combined with air-parcel back-trajectory simulations to determine the origin of air masses over the coastal ocean. Comparisons with satellite retrievals of atmospheric composition reveal the benefits and limitations of polar-orbit satellite observations in capturing variability in atmospheric pollution gradients over land-water boundaries.

Tzortziou, Maria↗

Toward the Next Generation of Air Quality Monitoring Indicators

This paper introduces an initiative to bridge the state of scientific knowledge on air pollution with the needs of policymakers and stakeholders to design the "next generation" of air quality indicators. As a first step this initiative assesses current monitoring and modeling associated with a number of important pollutants with an eye toward identifying knowledge gaps and scientific needs that are a barrier to reducing air pollution impacts on human and ecosystem health across the globe. Four outdoor air pollutants were considered e particulate matter, ozone, mercury, and Persistent Organic Pollutants (POPs) e because of their clear adverse impacts on human and ecosystem health and because of the availability of baseline data for assessment for each. While other papers appearing in this issue will address each pollutant separately, this paper serves as a summary of the initiative and presents recommendations for needed investments to provide improved measurement, monitoring, and modeling data for policyrelevant indicators. The ultimate goal of this effort is to enable enhanced public policy responses to air pollution by linking improved data and measurement methods to decision-making through the development of indicators that can allow policymakers to better understand the impacts of air pollution and, along with source attribution based on modeling and measurements, facilitate improved policies to solve it. The development of indicators represents a crucial next step in this process.

Particulate matter↗

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.↗

Tropospheric Ozone Increases over the Southern Africa Region: Bellwether for Rapid Growth in Southern Hemisphere Pollution?

Increases in free-tropospheric (FT) ozone based on ozonesonde records from the early 1990s through 2008 over two subtropical stations, Irene (near Pretoria, South Africa) and Réunion (21 deg. S, 55 deg. E; approx. 2800 km NE of Irene in the Indian Ocean), have been reported. Over Irene a large increase in the urban-influenced boundary layer (BL, 1.5-4 km) was also observed during the 18-year period, equivalent to 30%decade−1. Here we show that the Irene BL trend is at least partly due to a gradual change in the sonde launch times from early morning to the midday period. The FT ozone profiles over Irene in 1990-2007 are re-examined, filling in a 1995-1999 gap with ozone profiles taken during the Measurements of Ozone by Airbus In-service Aircraft (MOZAIC) project over nearby Johannesburg. A multivariate regression model that accounts for the annual ozone cycle, El Niño-Southern Oscillation (ENSO) and possible tropopause changes was applied to monthly averaged Irene data from 4 to 11 km and to 1992-2011 Réunion sonde data from 4 to 15 km. Statistically significant trends appear predominantly in the middle and upper troposphere (UT; 4-11 km over Irene, 4-15 km over Réunion) in winter (June-August), with increases 1 ppbv yr(exp. −1) over Irene and approx. 2 ppbv yr(exp. −1) over Réunion. These changes are equivalent to approx. 25 and 35-45%decade( exp. −1), respectively. Both stations also display smaller positive trends in summer, with a 45%decade(exp. −1) ozone increase near the tropopause over Réunion in December. To explain the ozone increases, we investigated a time series of dynamical markers, e.g., potential vorticity (PV) at 330-350 K. PV affects UT ozone over Irene in November-December but displays little relationship with ozone over Réunion. A more likely reason for wintertime FT ozone increases over Irene and Réunion appears to be long-range transport of growing pollution in the Southern Hemisphere. The ozone increases are consistent with trajectory origins of air parcels sampled by the sondes and with recent NOx emissions trends estimated for Africa, South America and Madagascar. For Réunion trajectories also point to sources from the eastern Indian Ocean and Asia.

Trends↗

Atmospheric Chemistry from Space: Present Status and Future Plans

One of the unqualified successes of the earth observation program is NASA's continuing monitoring of the ozone layer from space. This activity began in the early 70's with research instruments and continues to this day with the TOMS instrument series and the Upper Atmosphere Research Satellite. In the near future, NASA will be launching the EOS Aura spacecraft (launch mid-2003) which will continue our study of the chemical processes that produce stratospheric ozone depletion. In addition, Aura will begin the first global study of lower atmospheric air pollution including urban ozone, aerosols, nitrogen oxides and carbon monoxide. Atmospheric air pollution measurements from earth orbit involve the development of very high precision spectrometer technologies that have never been flown in space. Farther into the future, lower atmospheric ozone and aerosols may be monitored by space based lidars in low earth orbit, by sensors in geostationary orbit and by continuous limb observations instrument from the Lagrange point L2.

Schoeberl, Mark R.↗

Mobile Observations of Ozone and Aerosols in Alabama: Southeastern US Summer Pollution and Coastal Variability

We present a detailed analysis of measurements of ozone (O 3 ) and aerosols collected using multiple platforms and instruments during a 5-day mini-campaign in Alabama, for improving our understanding of the chemistry and air quality in the Southeastern United States. Our study features the first on-road O 3 lidar profiling on highways and the coordinated airborne observations that captured O 3 and aerosol structures associated with synoptic weather conditions, stratospheric intrusions, wildfire smoke transport, and enhancements in urban areas. The Doppler wind lidar data suggest that the vertical structures and variability of O 3 and aerosols at Dauphin Island, a coastal site in the Gulf of Mexico, were related to both the synoptic flow and local-scale land-sea breeze circulation. The onshore gulf breeze, which typically started in the afternoon, helped to quickly dilute air pollutants near the surface, resulting in large gradients toward inland areas. In contrast, gradients were much smaller on days without a gulf breeze. O 3 and humidity were highly anti-correlated in the lower free troposphere, but weakly anti-correlated in the planetary boundary layer (PBL) suggesting more complicated emissions and sink of O 3 in the PBL. Our on-road and airborne measurement strategies to quantify the vertical and horizontal chemical gradients will be useful for future geostationary satellite validation.

Shi Kuang↗

Intercontinental Transport of Air Pollution

The development of the global economy goes beyond raising our standards of living. We are in an ear of increasing environmental as well as economic interdependence. Long-range transport of anthropogenic atmospheric pollutants such as ozone, ozone precursors, airborne particles, heavy metals (such as mercury) and persistent organic pollutants are the four major types of pollution that are transported over intercontinental distances and have global environmental effects. The talk includes: 1) an overview of the international agreements related to intercontinental transport of air pollutants, 2) information needed for decision making, 3) overview of the past research on intercontinental transport of air pollutants - a North American's perspective, and 4) future research needs.

Rogers, David↗

Field Calibration Techniques used to Characterize the Radiometric Stability of the GEO-CAPE Airborne Simulator (GCAS)

The GEOstationary Coastal and Air Pollution Events (GEO-CAPE) Airborne Simulator (GCAS) was developed at NASA’s Goddard Space Flight Center (GSFC) and has flown in multiple field campaigns to perform mapping of the regional-scale EPA criteria pollutants nitrogen dioxide, ozone, and formaldehyde. GCAS will also participate invalidation campaigns for NASA’s Tropospheric Emissions: Monitoring POllution (TEMPO) mission and the Korean Geostationary Environment Monitoring Spectrometer (GEMS) mission, both scheduled to launch in the early 2020s. GCAS houses two commercial Offner-type grating spectrometers that measure backscattered solar spectral radiance from the near-ultraviolet to near-infrared at high spatial resolution (typically 250 meters at 8.5 kilometer altitude). These radiances are used to retrieve spatial and temporal distributions of trace gases relevant to the boundary layer and free tropospheric atmospheric chemistry cycles. In this paper, we describe the field calibration techniques employed to characterize the spectral and temporal radiometric stability of the system during its most recent deployment in the 2018 Long Island Sound Trace Ozone Study (LISTOS) field campaign. Overall measurement uncertainty, retrieval impacts, and lessons learned for future deployments will also be described.

NASA’s Tropospheric Emissions: Monitoring POllutio↗

Aura OMI Observations of Regional SO2 and NO2 Pollution Changes from 2005 to 2015

The Ozone Monitoring Instrument (OMI) onboard NASA's Aura satellite has been providing global observations of the ozone layer and key atmospheric pollutant gases, such as nitrogen dioxide (NO2) and sulfur dioxide (SO2), since October 2004. The data products from the same instrument provide consistent spatial and temporal coverage and permit the study of anthropogenic and natural emissions on local-to-global scales. In this paper, we examine changes in SO2 and NO2 over some of the world's most polluted industrialized regions during the first decade of OMI observations. In terms of regional pollution changes, we see both upward and downward trends, sometimes in opposite directions for NO2 and SO2, for different study areas. The trends are, for the most part, associated with economic and/or technological changes in energy use, as well as regional regulatory policies. Over the eastern US, both NO2 and SO2 levels decreased dramatically from 2005 to 2015, by more than 40 and 80 percent, respectively, as a result of both technological improvements and stricter regulations of emissions. OMI confirmed large reductions in SO2 over eastern Europe's largest coal-fired power plants after installation of flue gas desulfurization devices. The North China Plain has the world's most severe SO2 pollution, but a decreasing trend has been observed since 2011, with about a 50 percent reduction in 2012-2015, due to an economic slowdown and government efforts to restrain emissions from the power and industrial sectors. In contrast, India's SO2 and NO2 levels from coal power plants and smelters are growing at a fast pace, increasing by more than 100 and 50 percent, respectively, from 2005 to 2015. Several SO2 hot spots observed over the Persian Gulf are probably related to oil and gas operations and indicate a possible underestimation of emissions from these sources in bottom-up emission inventories. Overall, OMI observations have proved valuable in documenting rapid changes in air quality over different parts of the world during last decade. The baseline established during the first 11 years of OMI is indispensable for the interpretation of air quality measurements from current and future satellite atmospheric composition missions.

SO2 and NO2↗

Aura OMI observations of regional SO2 and NO2 pollution changes from 2005 to 2015

The Ozone Monitoring Instrument (OMI) onboard NASA's Aura satellite has been providing global observations of the ozone layer and key atmospheric pollutant gases, such as nitrogen dioxide (NO2/ and sulfur dioxide (SO2/, since October 2004. The data products from the same instrument provide consistent spatial and temporal coverage and permit the study of anthropogenic and natural emissions on local-to-global scales. In this paper, we examine changes in SO2 and NO2 over some of the world's most polluted industrialized regions during the first decade of OMI observations. In terms of regional pollution changes, we see both upward and downward trends, sometimes in opposite directions for NO2 and SO2, for different study areas. The trends are, for the most part, associated with economic and/or technological changes in energy use, as well as regional regulatory policies. Over the eastern US, both NO2 and SO2 levels decreased dramatically from 2005 to 2015, by more than 40 and 80 %, respectively, as a result of both technological improvements and stricter regulations of emissions. OMI confirmed large reductions in SO2 over eastern Europe's largest coal-fired power plants after installation of flue gas desulfurization devices. The North China Plain has the world's most severe SO2 pollution, but a decreasing trend has been observed since 2011, with about a 50% reduction in 2012- 2015, due to an economic slowdown and government efforts to restrain emissions from the power and industrial sectors. In contrast, India's SO2 and NO2 levels from coal power plants and smelters are growing at a fast pace, increasing by more than 100 and 50 %, respectively, from 2005 to 2015. Several SO2 hot spots observed over the Persian Gulf are probably related to oil and gas operations and indicate a possible underestimation of emissions from these sources in bottom-up emission inventories. Overall, OMI observations have proved valuable in documenting rapid changes in air quality over different parts of the world during last decade. The baseline established during the first 11 years of OMI is indispensable for the interpretation of air quality measurements from current and future satellite atmospheric composition missions.

Pollution trends↗

Vertical Profiling of Air Pollution at RAPCD

The interaction between local and regional pollution levels occurs at the interface of the Planetary Boundary Layer and the Free Troposphere. Measuring the vertical distribution of ozone, aerosols, and winds with high temporal and vertical resolution is essential to diagnose the nature of this interchange and ultimately for accurately forecasting ozone and aerosol pollution levels. The Regional Atmospheric Profiling Center for Discovery, RAPCD, was built and instrumented to address this critical issue. The ozone W DIAL lidar, Nd:YAG aerosol lidar, and 2.1 micron Doppler wind lidar, along with balloon- borne ECC ozonesondes form the core of the W C D instrumentation for addressing this problem. Instrumentation in the associated Mobile Integrated Profiling (MIPS) laboratory includes 91 5Mhz profiler, sodar, and ceilometer. The collocated Applied particle Optics and Radiometry (ApOR) laboratory hosts an FTIR along with MOUDI and optical particle counters. With MODELS-3 analysis by colleagues in the National Space Science and Technology Center on the UAH campus and the co- located National Weather Service Forecasting Office in Huntsville, AL we are developing a unique facility for advancing the state of the science of pollution forecasting.

Newchurch, Michael J.↗

Assessment and Applications of NASA Ozone Data Products Derived from Aura OMI-MLS Satellite Measurements in Context of the GMI Chemical Transport Model

Measurements from the Ozone Monitoring Instrument (OMI) and Microwave Limb Sounder (MLS), both onboard the Aura spacecraft, have been used to produce daily global maps of column and profile ozone since August 2004. Here we compare and evaluate three strategies to obtain daily maps of tropospheric and stratospheric ozone from OMI and MLS measurements: trajectory mapping, direct profile retrieval, and data assimilation. Evaluation is based upon an assessment that includes validation using ozonesondes and comparisons with the Global Modeling Initiative (GMI) chemical transport model (CTM). We investigate applications of the three ozone data products from near-decadal and inter-annual timescales to day-to-day case studies. Zonally averaged inter-annual changes in tropospheric ozone from all of the products in any latitude range are of the order 1-2 Dobson Units while changes (increases) over the 8-year Aura record investigated http://eospso.gsfc.nasa.gov/atbd-category/49 vary approximately 2-4 Dobson Units. It is demonstrated that all of the ozone products can measure and monitor exceptional tropospheric ozone events including major forest fire and pollution transport events. Stratospheric ozone during the Aura record has several anomalous inter-annual events including stratospheric warming split events in the Northern Hemisphere extra-tropics that are well captured using the data assimilation ozone profile product. Data assimilation with continuous daily global coverage and vertical ozone profile information is the best of the three strategies at generating a global tropospheric and stratospheric ozone product for science applications.

GMI↗

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↗

Observing low-altitude features in ozone concentrations in a shoreline environment via uncrewed aerial systems

Abstract. Ozone is a pollutant formed in the atmosphere by photochemical processes involving nitrogen oxides (NOx) and volatile organic compounds (VOCs) when exposed to sunlight. Tropospheric boundary layer ozone is regularly measured at ground stations and sampled infrequently through balloon, lidar, and crewed aircraft platforms, which have demonstrated characteristic patterns with altitude. Here, to better resolve vertical profiles of ozone within the atmospheric boundary layer, we developed and evaluated an uncrewed aircraft system (UAS) platform for measuring ozone and meteorological parameters of temperature, pressure, and humidity. To evaluate this approach, a UAS was flown with a portable ozone monitor and a meteorological temperature and humidity sensor to compare to tall tower measurements in northern Wisconsin. In June 2020, as a part of the WiscoDISCO20 campaign, a DJI M600 hexacopter UAS was flown with the same sensors to measure Lake Michigan shoreline ozone concentrations. This latter UAS experiment revealed a low-altitude structure in ozone concentrations in a shoreline environment showing the highest ozone at altitudes from 20–100 m a.g.l. These first such measurements of low-altitude ozone via a UAS in the Great Lakes region revealed a very shallow layer of ozone-rich air lying above the surface.

Meteorology & Atmospheric Sciences↗

A Madden-Julian Oscillation in Tropospheric Ozone

This is the first study to indicate a Madden-Julian Oscillation (MJO) in tropospheric ozone. Tropospheric ozone is derived using differential measurements of total column ozone and stratospheric column ozone measured from total ozone mapping spectrometer (TOMS) and microwave limb sounder (MLS) instruments. Two broad regions of significant MJO signal are identified in the tropics, one in the western Pacific and the other in the eastern Pacific. Over both regions, MJO variations in tropospheric ozone represent 5-10 Dobson Unit (DU) peak-to-peak anomalies. These variations are significant compared to mean background amounts of 20 DU or less over most of the tropical Pacific. MJO signals of this magnitude would need to be considered when investigating and interpreting particular pollution events since ozone is a precursor of the hydroxyl (OH) radical, the main oxidizing agent of pollutants in the lower atmosphere.

Ziemke, J. R.↗

Convective Transport to the Upper Troposphere and Lower Stratosphere Over the Asian Summer Monsoon as Observed During the 2022 ACCLIP Airborne Campaign

Deep convection in the Asian summer monsoon (ASM) rapidly transports boundary layer pollutants including ozone-depleting substances into the upper troposphere and lower stratosphere (UTLS). The confinement of the seasonal anticyclonic circulation in the UTLS over Asia initially traps the pollutants near the tropopause level, but air masses are subsequently transported throughout the global stratosphere and impact Earth’s climate. Characterizing the transport pathways and processes of these pollutants are critical for identifying source regions and quantifying regional contributions to global stratospheric concentrations. The Asian summer monsoon Chemical and Climate Impact Project (ACCLIP) was conducted in summer 2022 using two high-altitude aircraft (NSF NCAR Gulfstream V and the NASA WB-57) to obtain UTLS chemical composition and aerosol distribution for characterizing the impact of the ASM on global chemistry and climate. Backward trajectories from ACCLIP flight tracks were traced through time-varying, satellite-derived global convective cloud top altitude fields to investigate the convective air mass origins of the sampled air parcels. Analyses reveal that air masses lofted by convection within the ASM (South Asian summer monsoon) and near the edge of the of the ASM anticyclone (East Asian summer monsoon) contributed to the airborne observations. In this study, we present a summary of the transport statistics of UTLS air masses sampled during ACCLIP and discuss the implications of these results on our understanding of the role of ASM in global constituent transport.

Convective↗

History of Ozone Research: From Schonbein to the Present

In 1840, C.F. Schonbein recognized that the smell generated in several different electrical and chemical processes was a single substance. He named this substance "ozein" from the Greek for "to smell". This substance we know today as ozone. Several periods can be distinguished in the continued development of our understanding of ozone. Throughout the late 19th century, the identity and properties of ozone were established and described. Ozone was recognized to be a constituent of normal air and tests were established to measure its concentration. Its disinfectant properties were recognized. New methods were developed for making ozone in the laboratory. In 1879, ultraviolet spectroscopic techniques were applied to the measurement of the solar spectrum and it was discovered by Comu that the spectrum was cut off at about 300 nm wavelength. Hartley suggested, based on laboratory measurements, that this cutoff was due to ozone in the atmosphere which he correctly asserted was somewhere in the upper atmosphere. This began the period of development of the amount and distribution of ozone throughout the atmosphere. In 1930, Chapman put forward the first theory of the formation and destruction of ozone. By the mid-1960s it was becoming obvious that the description of the chemical loss term was inadequate. By the early 1970s the chemical destruction of ozone by the oxides of hydrogen, nitrogen, chlorine, and bromine was recognized as an essential element in the chemical balance determining the ozone concentration. Today, ozone is a broad research project which crosses the boundaries of traditional disciplines. Stratospheric ozone loss due to chlorofluorocarbons is a newsworthy item. The Antarctic ozone hole opens up every spring. The provisions of the Montreal Protocol were agreed upon by countries around the world and promise to reduce the future levels of ozone-destroying chlorine in the stratosphere. Ozone concentrations in polluted cities are a subject of local and national regulations to limit its potential for causing health problems and corrosive effects on materials. A lot is known about ozone but many new questions are still being developed.

Stolarski, Richard S.↗

Consequences of Insufficient Production of Temporary NOx Reservoirs on Ozone Production in Models During KORUS-AQ

The advent of geostationary satellites, starting with GEMS over South Korea, offer the potential for additional insight into urban air quality. In preparation for these satellites, the joint NIER-NASA KORUS-AQ field campaign in 2016 obtained a large dataset for understanding local air quality and the contribution of local emissions to ozone and PM2.5 pollution. Models partitioned NOx primarily into inorganic nitrate (HNO3 + nitrate aerosol) while observations suggest that acyl peroxy nitrates (PNs) should be an important sink. Models tended to produce ozone too efficiently, which may be due to insufficient alkyl/multifunctional nitrate (ANs) production. Models are unable to simulate the transport of NOx away from the urban center and its impact on ozone production downwind.

Katherine R Travis↗