The Korea-United States Air Quality (KORUS-AQ) field study was conducted during May–June 2016 to understand the factors controlling air quality in South Korea. Extensive aircraft and ground network observations from the campaign offer an opportunity to address issues in current air quality models and reduce model-observation disagreements. This study examines these issues using model evaluation against the KORUS-AQ observations and intercomparisons between models. Six regional and two global chemistry transport models using identical anthropogenic emissions participated in the model intercomparison study and were used to conduct air quality simulations focusing on ozone (O 3 ), aerosols, and their precursors for the campaign. Using the KORUSv5 emissions inventory, which has been updated from KORUSv1, the models successfully reproduced observed nitrogen oxides (NO x ) and volatile organic compounds mixing ratios in surface air, especially in the Seoul Metropolitan Area, but showed systematic low biases for carbon monoxide (CO), implying possible missing CO sources in the inventory in East Asia. Although the DC-8 aircraft-observed O 3 precursor mixing ratios were well captured by the models, simulated O 3 levels were lower than the observations in the free troposphere in part due to too low stratospheric O 3 influxes, especially in regional models. During the campaign, the synoptic meteorology played an important role in determining the observed variability of PM 2.5 (PM diameter ≤ 2.5 μm) concentrations in South Korea. The models successfully simulated the observed PM 2.5 variability with significant inorganic sulfate-nitrate-ammonium aerosols contribution, but failed to reproduce that of organic aerosols, causing a large inter-model variability. From the model evaluation, we find that an ensemble of model results, incorporating individual models with differing strengths and weaknesses, performs better than most individual models at representing observed atmospheric compositions for the campaign. Ongoing model development and evaluation, in close collaboration with emissions inventory development, are needed to improve air quality forecasting.

Our understanding of the processes that control the burden and budget of tropospheric ozone has changed dramatically over the last 60 years. Models are the key tools used to understand these changes, and these underscore that there are many processes important in controlling the tropospheric ozone budget. In this critical review, we assess our evolving understanding of these processes, both physical and chemical. We review model simulations from the International Global Atmospheric Chemistry Atmospheric Chemistry and Climate Model Intercomparison Project and Chemistry Climate Modelling Initiative to assess the changes in the tropospheric ozone burden and its budget from 1850 to 2010. Analysis of these data indicates that there has been significant growth in the ozone burden from 1850 to 2000 (approximately 43 ± 9%) but smaller growth between 1960 and 2000 (approximately 16 ± 10%) and that the models simulate burdens of ozone well within recent satellite estimates. The Chemistry Climate Modelling Initiative model ozone budgets indicate that the net chemical production of ozone in the troposphere plateaued in the 1990s and has not changed since then inspite of increases in the burden. There has been a shift in net ozone production in the troposphere being greatest in the northern mid and high latitudes to the northern tropics, driven by the regional evolution of precursor emissions. An analysis of the evolution of tropospheric ozone through the 21st century, as simulated by Climate Model Intercomparison Project Phase 5 models, reveals a large source of uncertainty associated with models themselves (i.e., in the way that they simulate the chemical and physical processes that control tropospheric ozone). This structural uncertainty is greatest in the near term (two to three decades), but emissions scenarios dominate uncertainty in the longer term (2050–2100) evolution of tropospheric ozone. This intrinsic model uncertainty prevents robust predictions of near-term changes in the tropospheric ozone burden, and we review how progress can be made to reduce this limitation.

Tropospheric ozone (O 3 ) is a greenhouse gas as well as a harmful air pollutant with adverse effects on human health and vegetation: The observation and attribution of its long-term variability are key activities to monitor the effectiveness of pollution reduction protocols. In this work, we present the analysis of multi-annual near-surface O 3 (1996–2016) at the Mt. Cimone (CMN, Italian northern Apennines) WMO/GAW global station and the comparison with two “reference” high-mountain sites in Europe: Jungfraujoch (JFJ, Swiss Alps) and Mt. Zugspitze (ZUG/ZSF, German Alps). Negative O 3 trends were observed at CMN over the period 1996–2016 (from –0.19 to –0.22 ppb yr –1 ), with the strongest tendencies as being observed for the warm months (May–September: –0.32 ppb yr –1 during daytime). The magnitude of the calculated O 3 trends at CMN are 2 times higher than those calculated for ZUG/ZSF and 3–4 times higher than for JFJ. With respect to JFJ and ZUG/ZSF, higher O 3 values were observed at CMN during 2004–2008, while good agreement is found for the remaining periods. We used Lagrangian simulations by the FLEXPART particle dispersion model and near-surface O 3 data over different European regions, for investigating the possibility that the appearance of the O 3 anomalies at CMN could be related to variability in the atmospheric transport or in near-surface O 3 over specific source regions. Even if it was not possible to achieve a general robust explanation for the occurrence of the high O 3 values at CMN during 2004–2008, the variability of (1) regional and long-range atmospheric transport at CMN and (2) European near-surface O 3 could motivate the observed anomalies in specific seasons and years. Interestingly, we found a long-term variability in air mass transport at JFJ with enhanced (decreased) contributions from Western European (intercontinental regions).

To understand the characteristics of air quality in the Seoul Metropolitan Area, intensive measurements were conducted under the Korea-United States Air Quality (KORUS-AQ) campaign. Trace gases such as O 3 , NO x , NO y , SO 2 , CO, and volatile organic compounds (VOCs), photochemical byproducts such as H 2 O 2 and HCHO, aerosol species, and meteorological variables including planetary boundary layer height were simultaneously measured at Olympic Park in Seoul. During the measurement period, high O 3 episodes that exceeded the 90 ppbv hourly maximum occurred on 14 days under four distinct synoptic meteorological conditions. Furthermore, local circulation such as land–sea breeze and diurnal evolution of the boundary layer were crucial in determining the concentrations of precursor gases, including NO x and VOC as well as O 3 . During such episodes, the nighttime NO x and VOC and daytime UV levels were higher compared to non-episode days. The overall precursor levels and photochemical activity were represented fairly well by variations in the HCHO, which peaked in the morning during the high O 3 episodes. This study revealed that toluene was the most abundant VOC in Seoul, and its concentration increased greatly with NO x due to the large local influence under stagnant conditions. When O 3 was highly elevated concurrently with PM 2.5 under dominant westerlies, NO x and VOCs were relatively lower and CO was noticeably higher than in other episodes. Additionally, the O 3 production efficiency was the highest due to a low NO x with the highest NO z /NO y ratio among the four episodes. When westerlies were dominant in transport-south episode, the nighttime concentration of O 3 remained as high as 40~50 ppbv due to the minimum level of NO x titration. Overall, the Seoul Metropolitan Area is at NO x -saturated and VOC-limited conditions, which was diagnosed by indicator species and VOC/NO x ratios.

The Seoul Metropolitan Area (SMA) has a population of 24 million and frequently experiences unhealthy levels of ozone (O 3 ). In this work, measurements taken during the Korea-United States Air Quality Study (KORUS-AQ, 2016) are used to explore regional gradients in O 3 and its chemical precursors, and an observationally-constrained 0-D photochemical box model is used to quantify key aspects of O 3 production including its sensitivity to precursor gases. Box model performance was evaluated by comparing modeled concentrations of select secondary species to airborne measurements. These comparisons indicate that the steady state assumption used in 0-D box models cannot describe select intermediate species, highlighting the importance of having a broad suite of trace gases as model constraints. When fully constrained, aggregated statistics of modeled O 3 production rates agreed with observed changes in O 3 , indicating that the box model was able to represent the majority of O 3 chemistry. Comparison of airborne observations between urban Seoul and a downwind receptor site reveal a positive gradient in O 3 coinciding with a negative gradient in NO x , no gradient in CH 2 O, and a slight positive gradient in modeled rates of O 3 production. Together, these observations indicate a radical-limited (VOC-limited) O 3 production environment in the SMA. Zero-out simulations identified C 7+ aromatics as the dominant VOC contributors to O 3 production, with isoprene and anthropogenic alkenes making smaller but appreciable contributions. Simulations of model sensitivity to decreases in NO x produced results that were not spatially uniform, with large increases in O 3 production predicted for urban Seoul and decreases in O 3 production predicted for far-outlying areas. The policy implications of this work are clear: Effective O 3 mitigation strategies in the SMA must focus on reducing local emissions of C 7+ aromatics, while reductions in NO x emissions may increase O 3 in some areas but generally decrease the regional extent of O 3 exposure.

We examine O 3 production and its sensitivity to precursor gases and boundary layer mixing in Korea by using a 3-D global chemistry transport model and extensive observations during the KORea-US cooperative Air Quality field study in Korea, which occurred in May–June 2016. During the campaign, observed aromatic species onboard the NASA DC-8 aircraft, especially toluene, showed high mixing ratios of up to 10 ppbv, emphasizing the importance of aromatic chemistry in O 3 production. To examine the role of VOCs and NO x in O 3 chemistry, we first implement a detailed aromatic chemistry scheme in the model, which reduces the normalized mean bias of simulated O 3 mixing ratios from –26% to –13%. Aromatic chemistry also increases the average net O 3 production in Korea by 37%. Corrections of daytime PBL heights, which are overestimated in the model compared to lidar observations, increase the net O 3 production rate by ~10%. In addition, increasing NO x emissions by 50% in the model shows best performance in reproducing O 3 production characteristics, which implies that NO x emissions are underestimated in the current emissions inventory. Sensitivity tests show that a 30% decrease in anthropogenic NO x emissions in Korea increases the O 3 production efficiency throughout the country, making rural regions ~2 times more efficient in producing O 3 per NO x consumed. Simulated O 3 levels overall decrease in the peninsula except for urban and other industrial areas, with the largest increase (~6 ppbv) in the Seoul Metropolitan Area (SMA). However, with simultaneous reductions in both NO x and VOCs emissions by 30%, O 3 decreases in most of the country, including the SMA. This implies the importance of concurrent emission reductions for both NO x and VOCs in order to effectively reduce O 3 levels in Korea.

Germany and the United Kingdom have domestic shale gas reserves which they may exploit in the future to complement their national energy strategies. However gas production releases volatile organic compounds (VOC) and nitrogen oxides (NO x ), which through photochemical reaction form ground-level ozone, an air pollutant that can trigger adverse health effects e.g. on the respiratory system. This study explores the range of impacts of a potential shale gas industry in these two countries on local and regional ambient ozone. To this end, comprehensive emission scenarios are used as the basis for input to an online-coupled regional chemistry transport model (WRF-Chem). Here we simulate shale gas scenarios over summer (June, July, August) 2011, exploring the effects of varying VOC emissions, gas speciation, and concentration of NO x emissions over space and time, on ozone formation. An evaluation of the model setup is performed, which exhibited the model’s ability to predict surface meteorological and chemical variables well compared with observations, and consistent with other studies. When different shale gas scenarios were employed, the results show a peak increase in maximum daily 8-hour average ozone from 3.7 to 28.3 μg m –3 . In addition, we find that shale gas emissions can force ozone exceedances at a considerable percentage of regulatory measurement stations locally (up to 21% in Germany and 35% in the United Kingdom) and in distant countries through long-range transport, and increase the cumulative health-related metric SOMO35 (maximum percent increase of ~28%) throughout the region. Findings indicate that VOC emissions are important for ozone enhancement, and to a lesser extent NO x , meaning that VOC regulation for a future European shale gas industry will be of especial importance to mitigate unfavorable health outcomes. Overall our findings demonstrate that shale gas production in Europe can worsen ozone air quality on both the local and regional scales.

From the earliest observations of ozone in the lower atmosphere in the 19th century, both measurement methods and the portion of the globe observed have evolved and changed. These methods have different uncertainties and biases, and the data records differ with respect to coverage (space and time), information content, and representativeness. In this study, various ozone measurement methods and ozone datasets are reviewed and selected for inclusion in the historical record of background ozone levels, based on relationship of the measurement technique to the modern UV absorption standard, absence of interfering pollutants, representativeness of the well-mixed boundary layer and expert judgement of their credibility. There are significant uncertainties with the 19th and early 20th-century measurements related to interference of other gases. Spectroscopic methods applied before 1960 have likely underestimated ozone by as much as 11% at the surface and by about 24% in the free troposphere, due to the use of differing ozone absorption coefficients. There is no unambiguous evidence in the measurement record back to 1896 that typical mid-latitude background surface ozone values were below about 20 nmol mol –1 , but there is robust evidence for increases in the temperate and polar regions of the northern hemisphere of 30–70%, with large uncertainty, between the period of historic observations, 1896–1975, and the modern period (1990–2014). Independent historical observations from balloons and aircraft indicate similar changes in the free troposphere. Changes in the southern hemisphere are much less. Regional representativeness of the available observations remains a potential source of large errors, which are difficult to quantify. The great majority of validation and intercomparison studies of free tropospheric ozone measurement methods use ECC ozonesondes as reference. Compared to UV-absorption measurements they show a modest (~1–5% ±5%) high bias in the troposphere, but no evidence of a change with time. Umkehr, lidar, and FTIR methods all show modest low biases relative to ECCs, and so, using ECC sondes as a transfer standard, all appear to agree to within one standard deviation with the modern UV-absorption standard. Other sonde types show an increase of 5–20% in sensitivity to tropospheric ozone from 1970–1995. Biases and standard deviations of satellite retrieval comparisons are often 2–3 times larger than those of other free tropospheric measurements. The lack of information on temporal changes of bias for satellite measurements of tropospheric ozone is an area of concern for long-term trend studies.

Data from ground-based ozone (O 3 ) vertical profiling platforms operated during the FRAPPE/DISCOVER-AQ campaigns in summer 2014 were used to characterize key processes responsible for establishing O 3 profile development in the boundary layer in the Northern Colorado Front Range. Morning mixing from the upper boundary layer and lower free troposphere into the lower boundary layer was the key process establishing the mid-morning boundary layer O 3 mixing ratio. Photochemical O 3 production throughout the boundary layer builds on the mid-morning profile. From late morning to mid-afternoon the continuing O 3 increase was nearly uniform through the depth of the profile measured by the tethersonde (~400 m). Ozonesondes flown on a near daily schedule over a four week period with multiple profiles on a number of days captured the full 1500 to 2000 m vertical extent of O 3 enhancements in the mixed boundary layer confirming O 3 production throughout the entire boundary layer. Continuous O 3 measurements from the Boulder Atmospheric Observatory (BAO) tall tower at 6 m and 300 m showed hourly O 3 at the 6 m level ≥75 ppb on 15% of the days. The diurnal variation on these days followed a pattern similar to that seen in the tethersonde profiles. The association of high O 3 days at the BAO tower with transport from sectors with intense oil and natural gas production toward the northeast suggests emissions from this industry were an important source of O 3 precursors and are crucial in producing peak O 3 events in the NCFR. Higher elevation locations to the west of the NCFR plains regularly experience higher O 3 values than those in the lower elevation NCFR locations. Exposure of populations in these areas is not captured by the current regulatory network, and likely underestimated in population O 3 exposure assessments.

The total solar eclipse on August 21, 2017, provided a rare opportunity to observe and test our understanding of atmospheric dynamics and photochemical dependency on solar irradiance. Here, we utilize observations from the continuous monitoring of both slow and fast photochemically reacting trace gases near Boulder, Colorado, for evaluating the unique dynamic and photochemical forcings on the eclipse day. The monitoring station saw a 93% solar obstruction during the peak of the eclipse. Eclipse day data are contrasted with the full month’s record from this site. The loss of irradiance caused cooling of the surface air by ~3°C, and weakened convective and turbulent mixing. This resulted in a buildup of slow photoreactive gases (methane, short-chain non-methane hydrocarbons), as well as total nitrogen oxides (the sum of nitric oxide (NO) + nitrogen dioxide (NO 2 )) in the surface layer. In contrast, ozone (O 3 ) declined by ~15 ppb during the first phase of the eclipse compared to median August diurnal mixing ratios. Similar O 3 signatures were observed at a series of network stations along the Northern Colorado Front Range. With the loss of irradiance, the initial ratio of NO/(NO + NO 2 ) of ~0.2 dropped steadily, bottoming out at <0.01, but rebounded to approximately two times above August median levels for this time of day towards the end of the eclipse. Above average O 3 enhancements were seen in the afternoon hours following the eclipse at this and a series of other nearby surface O 3 monitoring sites. The contrasting behavior of these slow and fast photoreactive gases, and comparison with other published eclipse data, allow characterizing these responses as more typical for an urban/polluted environment.

Ozone (O 3 ) is a key air pollutant that is produced from precursor emissions and has adverse impacts on human health and ecosystems. In the U.S., the Clean Air Act (CAA) regulates O 3 levels to protect public health and welfare, but unraveling the origins of surface O 3 is complicated by the presence of contributions from multiple sources including background sources like stratospheric transport, wildfires, biogenic precursors, and international anthropogenic pollution, in addition to U.S. anthropogenic sources. In this report, we consider more than 100 published studies and assess current knowledge on the spatial and temporal distribution, trends, and sources of background O 3 over the continental U.S., and evaluate how it influences attainment of the air quality standards. We conclude that spring and summer seasonal mean U.S. background O 3 (USB O 3 ), or O 3 formed from natural sources plus anthropogenic sources in countries outside the U.S., is greatest at high elevation locations in the western U.S., with monthly mean maximum daily 8-hour average (MDA8) mole fractions approaching 50 parts per billion (ppb) and annual 4 th highest MDA8s exceeding 60 ppb, at some locations. At lower elevation sites, e.g., along the West and East Coasts, seasonal mean MDA8 USB O 3 is in the range of 20–40 ppb, with generally smaller contributions on the highest O 3 days. The uncertainty in U.S. background O 3 is around ±10 ppb for seasonal mean values and higher for individual days. Noncontrollable O 3 sources, such as stratospheric intrusions or precursors from wildfires, can make significant contributions to O 3 on some days, but it is challenging to quantify accurately these contributions. We recommend enhanced routine observations, focused field studies, process-oriented modeling studies, and greater emphasis on the complex photochemistry in smoke plumes as key steps to reduce the uncertainty associated with background O 3 in the U.S.

This Tropospheric Ozone Assessment Report (TOAR) on the current state of knowledge of ozone metrics of relevance to vegetation ( TOAR-Vegetation ) reports on present-day global distribution of ozone at over 3300 vegetated sites and the long-term trends at nearly 1200 sites. TOAR-Vegetation focusses on three metrics over vegetation-relevant time-periods across major world climatic zones: M12, the mean ozone during 08:00–19:59; AOT40, the accumulation of hourly mean ozone values over 40 ppb during daylight hours, and W126 with stronger weighting to higher hourly mean values, accumulated during 08:00–19:59. Although the density of measurement stations is highly variable across regions, in general, the highest ozone values (mean, 2010–14) are in mid-latitudes of the northern hemisphere, including southern USA, the Mediterranean basin, northern India, north, north-west and east China, the Republic of Korea and Japan. The lowest metric values reported are in Australia, New Zealand, southern parts of South America and some northern parts of Europe, Canada and the USA. Regional-scale assessments showed, for example, significantly higher AOT40 and W126 values in East Asia (EAS) than Europe (EUR) in wheat growing areas ( p < 0.05), but not in rice growing areas. In NAM, the dominant trend during 1995–2014 was a significant decrease in ozone, whilst in EUR it was no change and in EAS it was a significant increase. TOAR-Vegetation provides recommendations to facilitate a more complete global assessment of ozone impacts on vegetation in the future, including: an increase in monitoring of ozone and collation of field evidence of the damaging effects on vegetation; an investigation of the effects on peri-urban agriculture and in mountain/upland areas; inclusion of additional pollutant, meteorological and inlet height data in the TOAR dataset; where not already in existence, establishing new region-specific thresholds for vegetation damage and an innovative integration of observations and modelling including stomatal uptake of the pollutant.

In the framework of the In Service Aircraft for Global Observing System (IAGOS) program, airborne in-situ O 3 and CO measurements are performed routinely using in-service aircraft, providing vertical profiles from the surface to about 10–12 km. Due to the specificity of IAGOS measurements (measurements around busy international airports), uncertainties exist on their representativeness in the lower troposphere as they may be impacted by emissions related to airport activities and/or other aircraft. In this study, we thus investigate how the IAGOS measurements in the lower troposphere compare with nearby surface stations (from the local Air Quality monitoring network (AQN)) and more distant regional surface stations (from the Global Atmospheric Watch (GAW) network). The study focuses on Frankfurt but some results at other European airports (Vienna, Paris) are also discussed. Results indicate that the IAGOS observations close to the surface do not appear to be strongly impacted by local emissions related to airport activities. In terms of mixing ratio distribution, seasonal variations and trends, the CO and O 3 mixing ratios measured by IAGOS in the first few hundred metres above the surface have similar characteristics to the mixing ratios measured at surrounding urban background stations. Higher in altitude, both the difference with data from the local AQN and the consistency with the GAW regional stations are higher, which indicates a larger representativeness of the IAGOS data. Despite few quantitative differences with Frankfurt, consistent results are obtained in the two other cities Vienna and Paris. Based on 11 years of data (2002–2012), this study thus demonstrates that IAGOS observations in the lowest troposphere can be used as a complement to surface stations to study the air quality in/around the agglomeration, providing important information on the vertical distribution of pollution.

This study quantifies the present-day global and regional distributions (2010–2014) and trends (2000–2014) for five ozone metrics relevant for short-term and long-term human exposure. These metrics, calculated by the Tropospheric Ozone Assessment Report, are: 4 th highest daily maximum 8-hour ozone (4MDA8); number of days with MDA8 > 70 ppb (NDGT70), SOMO35 (annual Sum of Ozone Means Over 35 ppb) and two seasonally averaged metrics (3MMDA1; AVGMDA8). These metrics were explored at ozone monitoring sites worldwide, which were classified as urban or non-urban based on population and nighttime lights data. Present-day distributions of 4MDA8 and NDGT70, determined predominantly by peak values, are similar with highest levels in western North America, southern Europe and East Asia. For the other three metrics, distributions are similar with North–South gradients more prominent across Europe and Japan. Between 2000 and 2014, significant negative trends in 4MDA8 and NDGT70 occur at most US and some European sites. In contrast, significant positive trends are found at many sites in South Korea and Hong Kong, with mixed trends across Japan. The other three metrics have similar, negative trends for many non-urban North American and some European and Japanese sites, and positive trends across much of East Asia. Globally, metrics at many sites exhibit non-significant trends. At 59% of all sites there is a common direction and significance in the trend across all five metrics, whilst 4MDA8 and NDGT70 have a common trend at ~80% of all sites. Sensitivity analysis shows AVGMDA8 trends differ with averaging period (warm season or annual). Trends are unchanged at many sites when a 1995–2014 period is used; although fewer sites exhibit non-significant trends. Over the longer period 1970–2014, most Japanese sites exhibit positive 4MDA8/SOMO35 trends. Insufficient data exist to characterize ozone trends for the rest of Asia and other world regions.

Instrumented aircraft measuring air composition in the Uinta Basin, Utah, during February 2012 and January-February 2013 documented dramatically different atmospheric ozone (O 3 ) mole fractions. In 2012 O 3 remained near levels of ∼40 ppb in a well-mixed 500–1000 m deep boundary layer while in 2013, O 3 mole fractions >140 ppb were measured in a shallow (∼200 m) boundary layer. In contrast to 2012 when mole fractions of emissions from oil and gas production such as methane (CH 4 ), non-methane hydrocarbons (NMHCs) and combustion products such as carbon dioxide (CO 2 ) were moderately elevated, in winter 2013 very high mole fractions were observed. Snow cover in 2013 helped produce and maintain strong temperature inversions that capped a shallow cold pool layer. In 2012, O 3 and CH 4 and associated NMHCs mole fractions were not closely related. In 2013, O 3 mole fractions were correlated with CH 4 and a suite of NMHCs identifying the gas field as the primary source of the O 3 precursor NMHC emissions. In 2013 there was a strong positive correlation between CH 4 and CO 2 suggesting combustion from oil and natural gas processing activities. The presence of O 3 precursor NMHCs through the depth of the boundary layer in 2013 led to O 3 production throughout the layer. In 2013, O 3 mole fractions increased over the course of the week-long episodes indicating O 3 photochemical production was larger than dilution and deposition rates, while CH 4 mole fractions began to level off after 3 days indicative of some air being mixed out of the boundary layer. The plume of a coal-fired power plant located east of the main gas field was not an important contributor to O 3 or O 3 precursors in the boundary layer in 2013.

Boundary layer atmospheric ozone depletion events (ODEs) are commonly observed across polar sea ice regions following polar sunrise. During March-April 2005 in Alaska, the coastal site of Barrow and inland site of Atqasuk experienced ODEs (O 3 < 10 nmol mol -1 ) concurrently for 31% of the observations, consistent with large spatial scale ozone depletion. However, 7% of the time ODEs were exclusively observed inland at Atqasuk. This phenomenon also occurred during one of nine flights during the BRomine, Ozone, and Mercury EXperiment (BROMEX), when atmospheric vertical profiles at both sites showed near-surface ozone depletion only at Atqasuk on 28 March 2012. Concurrent in-flight BrO measurements made using nadir scanning differential optical absorption spectroscopy (DOAS) showed the differences in ozone vertical profiles at these two sites could not be attributed to differences in locally occurring halogen chemistry. During both studies, backward air mass trajectories showed that the Barrow air masses observed had interacted with open sea ice leads, causing increased vertical mixing and recovery of ozone at Barrow and not Atqasuk, where the air masses only interacted with tundra and consolidated sea ice. These observations suggest that, while it is typical for coastal and inland sites to have similar ozone conditions, open leads may cause heterogeneity in the chemical composition of the springtime Arctic boundary layer over coastal and inland areas adjacent to sea ice regions.

In situ atmospheric ozone measurements aboard the R/V Ronald H. Brown during the 2008 Gas-Ex and AMMA research cruises were compared with data from four island and coastal Global Atmospheric Watch stations in the Atlantic Ocean to examine ozone transport in the marine boundary layer (MBL). Ozone measurements made at Tudor Hill, Bermuda, were subjected to continental outflow from the east coast of the United States, which resulted in elevated ozone levels above 50 ppbv. Ozone measurements at Cape Verde, Republic of Cape Verde, approached 40 ppbv in springtime and were influenced by outflow from Northern Africa. At Ragged Point, Barbados, ozone levels were ∼ 21 ppbv; back trajectories showed the source region to be the middle of the Atlantic Ocean. Ozone measurements from Ushuaia, Argentina, indicated influence from the nearby city; however, the comparison of the daily maxima ozone mole fractions measured at Ushuaia and aboard the Gas-Ex cruise revealed that these were representative of background ozone in higher latitudes of the Southern Hemisphere. Diurnal ozone cycles in the shipborne data, frequently reaching 6–7 ppbv, were larger than most previous reports from coastal or island monitoring locations and simulations based on HO x photochemistry alone. However, these data show better agreement with recent ozone modeling that included ozone-halogen chemistry. The transport time between station and ship was estimated from HYSPLIT back trajectories, and the change of ozone mole fractions during transport in the MBL was estimated. Three comparisons showed declining ozone levels; in the subtropical and tropical North Atlantic Ocean the loss of ozone was < 1.5 ppbv day −1 . Back trajectories at Ushuaia were too inconsistent to allow for this determination. Comparisons between ship and station measurements showed that ozone behavior and large-scale (∼ 1000 km) multi-day transport features were well retained during transport in the MBL.