Rapid ozone depletion after humidification of the stratosphere by the Hunga Tonga Eruption.

The eruption of the Hunga Tonga-Hunga Ha'apai volcano on 15 January 2022 offered a good opportunity to explore the early impacts of tropical volcanic eruptions on stratospheric composition. Balloon-borne observations near Réunion Island revealed the unprecedented amount of water vapor injected by the volcano. The enhanced stratospheric humidity, radiative cooling, and expanded aerosol surface area in the volcanic plume created the ideal conditions for swift ozone depletion of 5% in the tropical stratosphere in just 1 week. The decrease in hydrogen chloride by 0.4 parts per million by volume (ppbv) and the increase in chlorine monoxide by 0.4 ppbv provided compelling evidence for chlorine activation within the volcanic plume. This study enhances our understanding of the effect of this unusual volcanic eruption on stratospheric chemistry and provides insights into possible chemistry changes that may occur in a changing climate.

COVID-19 Crisis Reduces Free Tropospheric Ozone Across the Northern Hemisphere.

Throughout spring and summer 2020, ozone stations in the northern extratropics recorded unusually low ozone in the free troposphere. From April to August, and from 1 to 8 kilometers altitude, ozone was on average 7% (≈4 nmol/mol) below the 2000-2020 climatological mean. Such low ozone, over several months, and at so many stations, has not been observed in any previous year since at least 2000. Atmospheric composition analyses from the Copernicus Atmosphere Monitoring Service and simulations from the NASA GMI model indicate that the large 2020 springtime ozone depletion in the Arctic stratosphere contributed less than one-quarter of the observed tropospheric anomaly. The observed anomaly is consistent with recent chemistry-climate model simulations, which assume emissions reductions similar to those caused by the COVID-19 crisis. COVID-19 related emissions reductions appear to be the major cause for the observed reduced free tropospheric ozone in 2020.

Taehwa Research Forest: A receptor site for severe domestic pollution events in Korea during 2016.

During the May-June 2016 International Cooperative Air Quality Field Study in Korea (KORUS-AQ), light synoptic meteorological forcing facilitated Seoul metropolitan pollution outflow to reach the remote Taehwa Research Forest (TRF) site and cause regulatory exceedances of ozone on 24 days. Two of these severe pollution events are thoroughly examined. The first, occurring on 17 May 2016, tracks transboundary pollution transport exiting eastern China and the Yellow Sea, traversing the Seoul Metropolitan Area (SMA), and then reaching TRF in the afternoon hours with severely polluted conditions. This case study indicates that although outflow from China and the Yellow Sea were elevated with respect to chemically unperturbed conditions, the regulatory exceedance at TRF was directly linked in time, space, and altitude to urban Seoul emissions. The second case studied, occurring on 09 June 2016, reveals that increased levels of biogenic emissions, in combination with amplified urban emissions, were associated with severe levels of pollutions and a regulatory exceedance at TRF. In summary, domestic emissions may be causing more pollution than by trans-boundary pathways, which have been historically believed to be the major source of air pollution in South Korea. The case studies are assessed with multiple aircraft, model (photochemical and meteorological) simulations, in-situ chemical sampling, and extensive ground-based profiling at TRF. These observations clearly identify TRF and the surrounding rural communities as receptor sites for severe pollution events associated with Seoul outflow, which will result in long-term negative effects to both human health and agriculture in the affected areas.

Comparison of Near-surface NO2 Pollution with Pandora Total Column NO2 during the Korea-United States Ocean Color (KORUS OC) Campaign.

Near-surface air quality (AQ) observations over coastal waters are scarce, a situation that limits our capacity to monitor pollution events at land-water interfaces. Satellite measurements of total column (TC) nitrogen dioxide (NO2) observations are a useful proxy for combustion sources but the once daily snapshots available from most sensors are insufficient for tracking the diurnal evolution and transport of pollution. Ground-based remote sensors like the Pandora Spectrometer Instrument (PSI) that have been developed to verify space-based total column NO2 and other trace gases are being tested for routine use as certified AQ monitors. The KORUS-OC (Korea-United States Ocean Color) cruise aboard the R/V Onnuri in May-June 2016 represented an opportunity to study AQ near the South Korean coast, a region affected by both local/regional and long-distance pollution sources. Using PSI data in direct-sun mode and in situ sensors for shipboard ozone, CO and NO2, we explore, for the first time, relationships between TC NO2 and surface AQ in this coastal region. Three case studies illustrate the value of the PSI as well as complexities in the surface-column NO2 relationship caused by varying meteorological conditions. Case Study 1 (25-26 May 2016) exhibited a high correlation of surface NO2 to TC NO2 measured by both PSI and Aura's Ozone Monitoring Instrument (OMI) but two other cases displayed poor relationships between in situ and TC NO2 due to decoupling of pollution layers from the surface. With suitable interpretation the PSI TC NO2 measurement demonstrates good potential for working with upcoming geostationary satellites to advance diurnal tracking of pollution.

Ozonesonde Quality Assurance: The JOSIE-SHADOZ (2017) Experience.

The ozonesonde is a small balloon-borne instrument that is attached to a standard radiosonde to measure profiles of ozone from the surface to 35 km with ~100-m vertical resolution. Ozonesonde data constitute a mainstay of satellite calibration and are used for climatologies and analysis of trends, especially in the lower stratosphere where satellites are most uncertain. The electrochemical-concentration cell (ECC) ozonesonde has been deployed at ~100 stations worldwide since the 1960s, with changes over time in manufacture and procedures, including details of the cell chemical solution and data processing. As a consequence, there are biases among different stations and discontinuities in profile time-series from individual site records. For 22 years the Jülich [Germany] Ozone Sonde Intercomparison Experiment (JOSIE) has periodically tested ozonesondes in a simulation chamber designated the World Calibration Centre for Ozonesondes (WCCOS) by WMO. In October-November 2017 a JOSIE campaign evaluated the sondes and procedures used in SHADOZ (Southern Hemisphere Additional Ozonesondes), a 14-station sonde network operating in the tropics and subtropics. A distinctive feature of the 2017 JOSIE was that the tests were conducted by operators from eight SHADOZ stations. Experimental protocols for the SHADOZ sonde configurations, which represent most of those in use today, are described, along with preliminary results. SHADOZ stations that follow WMO-recommended protocols record total ozone within 3% of the JOSIE reference instrument. These results and prior JOSIEs demonstrate that regular testing is essential to maintain best practices in ozonesonde operations and to ensure high-quality data for the satellite and ozone assessment communities.

The Ozone Water-Land Environmental Transition Study (OWLETS): An Innovative Strategy for Understanding Chesapeake Bay Pollution Events.

Coastal regions have historically represented a significant challenge for air quality investigations due to water-land boundary transition characteristics and a paucity of measurements available over water. Prior studies have identified the formation of high levels of ozone over water bodies, such as the Chesapeake Bay, that can potentially recirculate back over land to significantly impact populated areas. Earth-observing satellites and forecast models face challenges in capturing the coastal transition zone where small-scale meteorological dynamics are complex and large changes in pollutants can occur on very short spatial and temporal scales. An observation strategy is presented to synchronously measure pollutants 'over-land' and 'over-water' to provide a more complete picture of chemical gradients across coastal boundaries for both the needs of state and local environmental management and new remote sensing platforms. Intensive vertical profile information from ozone lidar systems and ozonesondes, obtained at two main sites, one over land and the other over water, are complemented by remote sensing and in-situ observations of air quality from ground-based, airborne (both personned and unpersonned), and shipborne platforms. These observations, coupled with reliable chemical transport simulations, such as the NOAA National Air Quality Forecast Capability (NAQFC), are expected to lead to a more fully characterized and complete land-water interaction observing system that can be used to assess future geostationary air quality instruments, such as the NASA Tropospheric Emissions: Monitoring of Pollution (TEMPO) as well as current low earth orbiting satellites, such as the European Space Agency's Sentinel 5-Precursor (S5-P) with its Tropospheric Monitoring Instrument (TROPOMI).

Characterizing Global Ozonesonde Profile Variability from Surface to the UT/LS with a Clustering Technique and MERRA-2 Reanalysis.

Our previous studies employing the self-organizing map (SOM) clustering technique to ozonesonde data have found significant links among meteorological and chemical regimes, and the shape of the ozone (O3) profile from the troposphere to the lower stratosphere. These studies, which focused on specific northern hemisphere mid-latitude geographical regions, demonstrated the advantages of SOM clustering by quantifying O3 profile variability and the O3/meteorological correspondence. We expand SOM to a global set of ozonesonde profiles spanning 1980-present from 30 sites to summarize the connections among O3 profiles, meteorology, and chemistry, using the Modern-Era Retrospective Analysis for Research and Applications, version 2 (MERRA-2) reanalysis and other ancillary data. Four clusters of O3 mixing ratio profiles from the surface to the upper troposphere/lower stratosphere (UT/LS) are generated for each site, which show dominant profile shapes and typical seasonality (or lack thereof) that generally correspond to latitude (i.e. Tropical, Subtropical, Mid-Latitude, Polar). Examination of MERRA-2 output reveals a clear relationship among SOM clusters and covarying meteorological fields (geopotential height, potential vorticity, and tropopause height) for Polar and Mid-latitude sites. However, these relationships break down within ±30° latitude. Carbon monoxide satellite data, along with velocity potential, a proxy for convection, calculated from MERRA-2 wind fields assist characterization of the Tropical and Subtropical sites, where biomass burning and convective transport linked to the Madden-Julian Oscillation (MJO) dominate O3 variability. In addition to geophysical characterization of O3 profile variability, these results can be used to evaluate chemical transport model output and satellite measurements of O3.

Ozone Variability and Anomalies Observed during SENEX and SEAC4RS Campaigns in 2013.

Tropospheric ozone variability occurs because of multiple forcing factors including surface emission of ozone precursors, stratosphere-to-troposphere transport (STT), and meteorological conditions. Analyses of ozonesonde observations made in Huntsville, AL, during the peak ozone season (May to September) in 2013 indicate that ozone in the planetary boundary layer was significantly lower than the climatological average, especially in July and August when the Southeastern United States (SEUS) experienced unusually cool and wet weather. Because of a large influence of the lower stratosphere, however, upper-tropospheric ozone was mostly higher than climatology, especially from May to July. Tropospheric ozone anomalies were strongly anti-correlated (or correlated) with water vapor (or temperature) anomalies with a correlation coefficient mostly about 0.6 throughout the entire troposphere. The regression slopes between ozone and temperature anomalies for surface up to mid-troposphere are within 3.0-4.1 ppbv·K-1. The occurrence rates of tropospheric ozone laminae due to STT are ≥50% in May and June and about 30% in July, August and September suggesting that the stratospheric influence on free-tropospheric ozone could be significant during early summer. These STT laminae have a mean maximum ozone enhancement over the climatology of 52±33% (35±24 ppbv) with a mean minimum relative humidity of 2.3±1.7%.

Tropospheric ozonesonde profiles at long-term U.S. monitoring sites: 2. Links between Trinidad Head, CA, profile clusters and inland surface ozone measurements.

Much attention has been focused on the transport of ozone (O3) to the Western U.S., particularly given the latest revision of the National Ambient Air Quality Standard (NAAQS) to 70 parts per billion by volume (ppbv) of O3. This makes defining a "background" O3 amount essential so that the effects of stratosphere-to-troposphere exchange and pollution transport to this region can be quantified. To evaluate free-tropospheric and surface O3 in the Western U.S., we use self-organizing maps to cluster 18 years of ozonesonde profiles (940 samples) from Trinidad Head, CA. Two of nine O3 mixing ratio profile clusters exhibit thin laminae of high O3 above Trinidad Head. A third, consisting of background (~20 - 40 ppbv) O3, occurs in ~10% of profiles. The high O3 layers are located between 1 and 4 km amsl, and reside above a subsidence inversion associated with a northern location of the semi-permanent Pacific subtropical high. Several ancillary data sets are examined to identify the high O3 sources (reanalyses, trajectories, remotely-sensed carbon monoxide), but distinguishing chemical and stratospheric influences of the elevated O3 is difficult. There is marked and long-lasting impact of the elevated tropospheric O3 on high-altitude surface O3 monitors at Lassen Volcanic and Yosemite National Parks, and Truckee, CA. Days corresponding to the high O3 clusters exhibit hourly surface O3 anomalies of +5 - 10 ppbv compared to a climatology; the anomalies can last up to four days. The profile and surface O3 links demonstrate the importance of regular ozonesonde profiling at Trinidad Head.

CAMx Ozone Source Attribution in the Eastern United States using Guidance from Observations during DISCOVER-AQ Maryland.

A Comprehensive Air-Quality Model with Extensions (CAMx) version 6.10 simulation was assessed through comparison with data acquired during NASA's 2011 DISCOVER-AQ Maryland field campaign. Comparisons for the baseline simulation (CB05 chemistry, EPA 2011 National Emissions Inventory) show a model overestimate of NOy by +86.2% and an underestimate of HCHO by -28.3%. We present a new model framework (CB6r2 chemistry, MEGAN v2.1 biogenic emissions, 50% reduction in mobile NOx, enhanced representation of isoprene nitrates) that better matches observations. The new model framework attributes 31.4% more surface ozone in Maryland to electric generating units (EGUs) and 34.6% less ozone to on-road mobile sources. Surface ozone becomes more NOx-limited throughout the eastern United States compared to the baseline simulation. The baseline model therefore likely underestimates the effectiveness of anthropogenic NOx reductions as well as the current contribution of EGUs to surface ozone.

Tropospheric ozonesonde profiles at long-term U.S. monitoring sites: 1. A climatology based on self-organizing maps.

Sonde-based climatologies of tropospheric ozone (O3) are vital for developing satellite retrieval algorithms and evaluating chemical transport model output. Typical O3 climatologies average measurements by latitude or region, and season. Recent analysis using self-organizing maps (SOM) to cluster ozonesondes from two tropical sites found clusters of O3 mixing ratio profiles are an excellent way to capture O3 variability and link meteorological influences to O3 profiles. Clusters correspond to distinct meteorological conditions, e.g. convection, subsidence, cloud cover, and transported pollution. Here, the SOM technique is extended to four long-term U.S. sites (Boulder, CO; Huntsville, AL; Trinidad Head, CA; Wallops Island, VA) with 4530 total profiles. Sensitivity tests on k-means algorithm and SOM justify use of 3×3 SOM (nine clusters). At each site, SOM clusters together O3 profiles with similar tropopause height, 500 hPa height/temperature, and amount of tropospheric and total column O3. Cluster means are compared to monthly O3 climatologies. For all four sites, near-tropopause O3 is double (over +100 parts per billion by volume; ppbv) the monthly climatological O3 mixing ratio in three clusters that contain 13 - 16% of profiles, mostly in winter and spring. Large mid-tropospheric deviations from monthly means (-6 ppbv, +7 - 10 ppbv O3 at 6 km) are found in two of the most populated clusters (combined 36 - 39% of profiles). These two clusters contain distinctly polluted (summer) and clean O3 (fall-winter, high tropopause) profiles, respectively. As for tropical profiles previously analyzed with SOM, O3 averages are often poor representations of U.S. O3 profile statistics.

Bay breeze influence on surface ozone at Edgewood, MD during July 2011.

Surface ozone (O3) was analyzed to investigate the role of the bay breeze on air quality at two locations in Edgewood, Maryland (lat: 39.4°, lon: -76.3°) for the month of July 2011. Measurements were taken as part of the first year of NASA's "Deriving Information on Surface Conditions from Column and Vertically Resolved Observations Relevant to Air Quality" (DISCOVER-AQ) Earth Venture campaign and as part of NASA's Geostationary for Coastal and Air Pollution Events Chesapeake Bay Oceanographic campaign with DISCOVER-AQ (Geo-CAPE CBODAQ). Geo-CAPE CBODAQ complements DISCOVER-AQ by providing ship-based observations over the Chesapeake Bay. A major goal of DISCOVER-AQ is determining the relative roles of sources, photochemistry and local meteorology during air quality events in the Mid-Atlantic region of the U.S. Surface characteristics, transport and vertical structures of O3 during bay breezes were identified using in-situ surface, balloon and aircraft data, along with remote sensing equipment. Localized late day peaks in O3 were observed during bay breeze days, maximizing an average of 3 h later compared to days without bay breezes. Of the 10 days of July 2011 that violated the U.S. Environmental Protection Agency (EPA) 8 h O3 standard of 75 parts per billion by volume (ppbv) at Edgewood, eight exhibited evidence of a bay breeze circulation. The results indicate that while bay breezes and the processes associated with them are not necessary to cause exceedances in this area, bay breezes exacerbate poor air quality that sustains into the late evening hours at Edgewood. The vertical and horizontal distributions of O3 from the coastal Edgewood area to the bay also show large gradients that are often determined by boundary layer stability. Thus, developing air quality models that can sufficiently resolve these dynamics and associated chemistry, along with more consistent monitoring of O3 and meteorology on and along the complex coastline of Chesapeake Bay must be a high priority.

Ozone correlations between mid-tropospheric partial columns and the near-surface at two mid-atlantic sites during the DISCOVER-AQ campaign in July 2011.

The current network of ground-based monitors for ozone (O3) is limited due to the spatial heterogeneity of O3 at the surface. Satellite measurements can provide a solution to this limitation, but the lack of sensitivity of satellites to O3 within the boundary layer causes large uncertainties in satellite retrievals at the near-surface. The vertical variability of O3 was investigated using ozonesondes collected as part of NASA's Deriving Information on Surface Conditions from COlumn and VERtically Resolved Observations Relevant to Air Quality (DISCOVER-AQ) campaign during July 2011 in the Baltimore, MD/Washington D.C. metropolitan area. A subset of the ozonesonde measurements was corrected for a known bias from the electrochemical solution strength using new procedures based on laboratory and field tests. A significant correlation of O3 over the two sites with ozonesonde measurements (Edgewood and Beltsville, MD) was observed between the mid-troposphere (7-10 km) and the near-surface (1-3 km). A linear regression model based on the partial column amounts of O3 within these subregions was developed to calculate the near-surface O3 using mid-tropospheric satellite measurements from the Tropospheric Emission Spectrometer (TES) onboard the Aura spacecraft. The uncertainties of the calculated near-surface O3 using TES mid-tropospheric satellite retrievals and a linear regression model were less than 20 %, which is less than that of the observed variability of O3 at the surface in this region. These results utilize a region of the troposphere to which existing satellites are more sensitive compared to the boundary layer and can provide information of O3 at the near-surface using existing satellite infrastructure and algorithms.

Ozone profiles in the Baltimore-Washington region (2006-2011): satellite comparisons and DISCOVER-AQ observations.

Much progress has been made in creating satellite products for tracking the pollutants ozone and NO2 in the troposphere. Yet, in mid-latitude regions where meteorological interactions with pollutants are complex, accuracy can be difficult to achieve, largely due to persistent layering of some constituents. We characterize the layering of ozone soundings and related species measured from aircraft over two ground sites in suburban Washington, DC (Beltsville, MD, 39.05 N; 76.9 W) and Baltimore (Edgewood, MD, 39.4 N; 76.3 W) during the July 2011 DISCOVER-AQ (Deriving Information on Surface Conditions from Column and Vertically Resolved Observations Relevant to Air Quality) experiment. First, we compare column-ozone amounts from the Beltsville and Edgewood sondes with data from overpassing satellites. Second, processes influencing ozone profile structure are analyzed using Laminar Identification and tracers: sonde water vapor, aircraft CO and NOy. Third, Beltsville ozone profiles and meteorological influences in July 2011 are compared to those from the summers of 2006-2010. Sonde-satellite offsets in total ozone during July 2011 at Edgewood and Beltsville, compared to the Ozone Monitoring Instrument (OMI), were 3 % mean absolute error, not statistically significant. The disagreement between an OMI/Microwave Limb Sounder-based tropospheric ozone column and the sonde averaged 10 % at both sites, with the sonde usually greater than the satellite. Laminar Identification (LID), that distinguishes ozone segments influenced by convective and advective transport, reveals that on days when both stations launched ozonesondes, vertical mixing was stronger at Edgewood. Approximately half the lower free troposphere sonde profiles have very dry laminae, with coincident aircraft spirals displaying low CO (80-110 ppbv), suggesting stratospheric influence. Ozone budgets at Beltsville in July 2011, determined with LID, as well as standard meteorological indicators, resemble those of 4 of the previous 5 summers. The penetration of stratospheric air throughout the troposphere appears to be typical for summer conditions in the Baltimore-Washington region.

Bay breeze climatology at two sites along the Chesapeake bay from 1986-2010: Implications for surface ozone.

Hourly surface meteorological measurements were coupled with surface ozone (O3) mixing ratio measurements at Hampton, Virginia and Baltimore, Maryland, two sites along the Chesapeake Bay in the Mid-Atlantic United States, to examine the behavior of surface O3 during bay breeze events and quantify the impact of the bay breeze on local O3 pollution. Analyses were performed for the months of May through September for the years 1986 to 2010. The years were split into three groups to account for increasingly stringent environmental regulations that reduced regional emissions of nitrogen oxides (NOx): 1986-1994, 1995-2002, and 2003-2010. Each day in the 25-year record was marked either as a bay breeze day, a non-bay breeze day, or a rainy/cloudy day based on the meteorological data. Mean eight hour (8-h) averaged surface O3 values during bay breeze events were 3 to 5 parts per billion by volume (ppbv) higher at Hampton and Baltimore than on non-bay breeze days in all year periods. Anomalies from mean surface O3 were highest in the afternoon at both sites during bay breeze days in the 2003-2010 study period. In conjunction with an overall lowering of baseline O3 after the 1995-2002 period, the percentage of total exceedances of the Environmental Protection Agency (EPA) 75 ppbv 8-h O3 standard that occurred on bay breeze days increased at Hampton for 2003-2010, while remaining steady at Baltimore. These results suggest that bay breeze circulations are becoming more important to causing exceedance events at particular sites in the region, and support the hypothesis of Martins et al. (2012) that highly localized meteorology increasingly drives air quality events at Hampton.