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Ozone in the troposphere affects humans and ecosystems as a pollutant and as a greenhouse gas. Observing, understanding and modelling this dual role, as well as monitoring effects of international regulations on air quality and climate change, however, challenge measurement systems to operate at opposite ends of the spatio-temporal scale ladder. Aboard the ESA/EU Copernicus Sentinel-5 Precursor (S5P) satellite launched in October 2017, the TROPOspheric Monitoring Instrument (TROPOMI) aspires to take the next leap forward by measuring ozone and its precursors at unprecedented horizontal resolution until at least the mid-2020s. In this work, we assess the quality of TROPOMI's first release (V01.01.05–08) of tropical tropospheric ozone column (TrOC) data. Derived with the convective cloud differential (CCD) method, TROPOMI daily TrOC data represent the 3 d moving mean ozone column between the surface and 270 hPa under clear-sky conditions gridded at 0.5∘ latitude by 1∘ longitude resolution. Comparisons to almost 2 years of co-located SHADOZ ozonesonde and satellite data (Aura OMI and MetOp-B GOME-2) conclude to TROPOMI biases between −0.1 and +2.3 DU (<+13 %) when averaged over the tropical belt. The field of the bias is essentially uniform in space (deviations DU) and stable in time at the 1.5–2.5 DU level. However, the record is still fairly short, and continued monitoring will be key to clarify whether observed patterns and stability persist, alter behaviour or disappear. Biases are partially due to TROPOMI and the reference data records themselves, but they can also be linked to systematic effects of the non-perfect co-locations. Random uncertainty due to co-location mismatch contributes considerably to the 2.6–4.6 DU (∼14 %–23 %) statistical dispersion observed in the difference time series. We circumvent part of this problem by employing the triple co-location analysis technique and infer that TROPOMI single-measurement precision is better than 1.5–2.5 DU (∼8 %–13 %), in line with uncertainty estimates reported in the data files. Hence, the TROPOMI precision is judged to be 20 %–25 % better than for its predecessors OMI and GOME-2B, while sampling at 4 times better spatial resolution and almost 2 times better temporal resolution. Using TROPOMI tropospheric ozone columns at maximal resolution nevertheless requires consideration of correlated errors at small scales of up to 5 DU due to the inevitable interplay of satellite orbit and cloud coverage. Two particular types of sampling error are investigated, and we suggest how these can be identified or remedied. Our study confirms that major known geophysical patterns and signals of the tropical tropospheric ozone field are imprinted in TROPOMI's 2-year data record. These include the permanent zonal wave-one pattern, the pervasive annual and semiannual cycles, the high levels of ozone due to biomass burning around the Atlantic basin, and enhanced convective activity cycles associated with the Madden–Julian Oscillation over the Indo-Pacific warm pool. TROPOMI's combination of higher precision and higher resolution reveals details of these patterns and the processes involved, at considerably smaller spatial and temporal scales and with more complete coverage than contemporary satellite sounders. If the accuracy of future TROPOMI data proves to remain stable with time, these hold great potential to be included in Climate Data Records, as well as serve as a travelling standard to interconnect the upcoming constellation of air quality satellites in geostationary and low Earth orbits.

The electrochemical concentration cell (ECC) ozonesonde has been the main instrument for in situ profiling of ozone worldwide; yet, some details of its operation, which contribute to the ozone uncertainty budget, are not well understood. Here, we investigate the time response of the chemical reactions inside the ECC and how corrections can be used to remove some systematic biases. The analysis is based on the understanding that two reaction pathways involving ozone occur inside the ECC that generate electrical currents on two very different timescales. The main fast-reaction pathway with a time constant of about 20 s is due the conversion of iodide to molecular iodine and the generation of two free electrons per ozone molecule. A secondary slow-reaction pathway involving the buffer generates an excess current of about 2 %–10 % with a time constant of about 25 min. This excess current can be interpreted as what has conventionally been considered the “background current”. This contribution can be calculated and removed from the measured current instead of the background current. Here we provide an algorithm to calculate and remove the contribution of the slow-reaction pathway and to correct for the time lag of the fast-reaction pathway. This processing algorithm has been applied to ozonesonde profiles at Costa Rica and during the Central Equatorial Pacific Experiment (CEPEX) as well as to laboratory experiments evaluating the performance of ECC ozonesondes. At Costa Rica, where a 1 % KI, 1/10th buffer solution is used, there is no change in the derived total ozone column; however, in the upper troposphere and lower stratosphere, average reported ozone concentrations increase by up to 7 % and above 30 km decrease by up to 7 %. During CEPEX, where a 1 % KI, full-buffer solution was used, ozone concentrations are increased mostly in the upper troposphere, with no change near the top of the profile. In the laboratory measurements, the processing algorithms have been applied to measurements using the majority of current sensing solutions and using only the stronger pump efficiency correction reported by Johnson et al. (2002). This improves the accuracy of the ECC sonde ozone profiles, especially for low ozone concentrations or large ozone gradients and removes systematic biases relative to the reference instruments. In the surface layer, operational procedures prior to launch, in particular the use of filters, influence how typical gradients above the surface are detected. The correction algorithm may report gradients that are steeper than originally reported, but their uncertainty is strongly influenced by the prelaunch procedures.

Ozone is a key constituent of the troposphere, where it drives photochemical processes, impacts air quality, and acts as a climate forcer. Large-scale in situ observations of ozone commensurate with the grid resolution of current Earth system models are necessary to validate model outputs and satellite retrievals. In this paper, we examine measurements from the Atmospheric Tomography (ATom; four deployments in 2016–2018) and the HIAPER Pole-to-Pole Observations (HIPPO; five deployments in 2009–2011) experiments, two global-scale airborne campaigns covering the Pacific and Atlantic basins. ATom and HIPPO represent the first global-scale, vertically resolved measurements of O3 distributions throughout the troposphere, with HIPPO sampling the atmosphere over the Pacific and ATom sampling both the Pacific and Atlantic. Given the relatively limited temporal resolution of these two campaigns, we first compare ATom and HIPPO ozone data to longer-term observational records to establish the representativeness of our dataset. We show that these two airborne campaigns captured on average 53 %, 54 %, and 38 % of the ozone variability in the marine boundary layer, free troposphere, and upper troposphere–lower stratosphere (UTLS), respectively, at nine well-established ozonesonde sites. Additionally, ATom captured the most frequent ozone concentrations measured by regular commercial aircraft flights in the northern Atlantic UTLS. We then use the repeated vertical profiles from these two campaigns to confirm and extend the existing knowledge of tropospheric ozone spatial and vertical distributions throughout the remote troposphere. We highlight a clear hemispheric gradient, with greater ozone in the Northern Hemisphere, consistent with greater precursor emissions and consistent with previous modeling and satellite studies. We also show that the ozone distribution below 8 km was similar in the extra-tropics of the Atlantic and Pacific basins, likely due to zonal circulation patterns. However, twice as much ozone was found in the tropical Atlantic as in the tropical Pacific, due to well-documented dynamical patterns transporting continental air masses over the Atlantic. Finally, we show that the seasonal variability of tropospheric ozone over the Pacific and the Atlantic basins is driven year-round by transported continental plumes and photochemistry, and the vertical distribution is driven by photochemistry and mixing with stratospheric air. This new dataset provides additional constraints for global climate and chemistry models to improve our understanding of both ozone production and loss processes in remote regions, as well as the influence of anthropogenic emissions on baseline ozone.

Past studies have suggested that ozone in the troposphere has increased globally throughout much of the 20th century due to increases in anthropogenic emissions and transport. We show, by combining satellite measurements with a chemical transport model, that during the last four decades tropospheric ozone does indeed indicate increases that are global in nature, yet still highly regional. Satellite ozone measurements from Nimbus-7 and Earth Probe Total Ozone Mapping Spectrometer (TOMS) are merged with ozone measurements from the Aura Ozone Monitoring Instrument/Microwave Limb Sounder (OMI/MLS) to determine trends in tropospheric ozone for 1979–2016. Both TOMS (1979–2005) and OMI/MLS (2005–2016) depict large increases in tropospheric ozone from the Near East to India and East Asia and further eastward over the Pacific Ocean. The 38-year merged satellite record shows total net change over this region of about +6 to +7 Dobson units (DU) (i.e., ∼15 %–20 % of average background ozone), with the largest increase (∼4 DU) occurring during the 2005–2016 Aura period. The Global Modeling Initiative (GMI) chemical transport model with time-varying emissions is used to aid in the interpretation of tropospheric ozone trends for 1980–2016. The GMI simulation for the combined record also depicts the greatest increases of +6 to +7 DU over India and East Asia, very similar to the satellite measurements. In regions of significant increases in tropospheric column ozone (TCO) the trends are a factor of 2–2.5 larger for the Aura record when compared to the earlier TOMS record; for India and East Asia the trends in TCO for both GMI and satellite measurements are ∼+3 DU decade−1 or greater during 2005–2016 compared to about +1.2 to +1.4 DU decade−1 for 1979–2005. The GMI simulation and satellite data also reveal a tropospheric ozone increases in ∼+4 to +5 DU for the 38-year record over central Africa and the tropical Atlantic Ocean. Both the GMI simulation and satellite-measured tropospheric ozone during the latter Aura time period show increases of ∼+3 DU decade−1 over the N Atlantic and NE Pacific.

NOAA's program of long-term monitoring of the vertical distribution of ozone with electrochemical concentration cell (ECC) ozonesondes has undergone a number of changes over the 50-year record. In order to produce a homogenous data set, these changes must be documented and, where necessary, appropriate corrections applied. This is the first comprehensive and consistent reprocessing of NOAA's ozonesonde data records that corrects for these changes using the rawest form of the data (cell current and pump temperature) in native resolution as well as a point-by-point uncertainty calculation that is unique to each sounding. The reprocessing is carried out uniformly at all eight ozonesonde sites in NOAA's network with differences in sensing solution and ozonesonde types accounted for in the same way at all sites. The corrections used to homogenize the NOAA ozonesonde data records greatly improve the ozonesonde measurements with an average one sigma uncertainty of ±4–6 % in the stratosphere and ±5–20 % in the troposphere. A comparison of the integrated column ozone from the ozonesonde profile with co-located Dobson spectrophotometers total column ozone measurements shows agreement within ±5 % for > 70 % of the profiles. Very good agreement is also found in the stratosphere between ozonesonde profiles and profiles retrieved from the Solar Backscatter Ultraviolet (SBUV) instruments.

We validate the Ozone Monitoring Instrument (OMI) Ozone Profile (PROFOZ) product from October 2004 through December 2014 retrieved by the Smithsonian Astrophysical Observatory (SAO) algorithm against ozonesonde observations. We also evaluate the effects of OMI row anomaly (RA) on the retrieval by dividing the dataset into before and after the occurrence of serious OMI RA, i.e., pre-RA (2004–2008) and post-RA (2009–2014). The retrieval shows good agreement with ozonesondes in the tropics and midlatitudes and for pressure ∼ 50 hPa after applying OMI averaging kernels to ozonesonde data. The MBs of the stratospheric ozone column (SOC, the ozone column from the tropopause pressure to the ozonesonde burst pressure) are within 2 % with SDs of ∼ 50 hPa. The SOC MBs increase up to 3 % with SDs as great as 6 % and the TOC SDs increase up to 30 %. The comparison generally degrades at larger solar zenith angles (SZA) due to weaker signals and additional sources of error, leading to worse performance at high latitudes and during the midlatitude winter. Agreement also degrades with increasing cloudiness for pressure > ∼ 100 hPa and varies with cross-track position, especially with large MBs and SDs at extreme off-nadir positions. In the tropics and midlatitudes, the post-RA comparison is considerably worse with larger SDs reaching 2 % in the stratosphere and 8 % in the troposphere and up to 6 % in TOC. There are systematic differences that vary with latitude compared to the pre-RA comparison. The retrieval comparison demonstrates good long-term stability during the pre-RA period but exhibits a statistically significant trend of 0.14–0.7 % year−1 for pressure −1 in SOC, and −0. 33 DU year−1 in TOC during the post-RA period. The spatiotemporal variation of retrieval performance suggests the need to improve OMI's radiometric calibration especially during the post-RA period to maintain the long-term stability and reduce the latitude/season/SZA and cross-track dependency of retrieval quality.

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° S, 55° E; ~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−1 over Irene and ~2 ppbv yr−1 over Réunion. These changes are equivalent to ~25 and 35–45% decade−1, respectively. Both stations also display smaller positive trends in summer, with a 45% decade−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.

A global climatology of tropospheric and stratospheric column ozone is derived by combining six years of Aura Ozone Monitoring Instrument (OMI) and Microwave Limb Sounder (MLS) ozone measurements for the period October 2004 through December 2010. The OMI/MLS tropospheric ozone climatology exhibits large temporal and spatial variability which includes ozone accumulation zones in the tropical south Atlantic year-round and in the subtropical Mediterranean/Asia region in summer months. High levels of tropospheric ozone in the Northern Hemisphere also persist in mid-latitudes over the eastern part of the North American continent extending across the Atlantic Ocean and the eastern part of the Asian continent extending across the Pacific Ocean. For stratospheric ozone climatology from MLS, largest column abundance is in the Northern Hemisphere in the latitude range 70° N–80° N in February–April and in the Southern Hemisphere around 40° S–50° S during August–October. Largest stratospheric ozone lies in the Northern Hemisphere and extends from the eastern Asian continent eastward across the Pacific Ocean and North America. With the advent of many newly developing 3-D chemistry and transport models it is advantageous to have such a dataset for evaluating the performance of the models in relation to dynamical and photochemical processes controlling the ozone distributions in the troposphere and stratosphere. The OMI/MLS gridded ozone climatology data are made available to the science community via the NASA Goddard Space Flight Center ozone and air quality website http://ozoneaq.gsfc.nasa.gov/.

Wildfires raged throughout western Russia and parts of Eastern Europe during a persistent heat wave in the summer of 2010. Anomalously high surface temperatures (35–41 °C) and low relative humidity (9–25 %) from mid-June to mid-August 2010 shown by analysis of radiosonde data from multiple sites in western Russia were ideal conditions for the wildfires to thrive. Measurements of outgoing longwave radiation (OLR) from the Atmospheric Infrared Sounder (AIRS) over western Russian indicate persistent subsidence during the heat wave. Daily three-day back-trajectories initiated over Moscow reveal a persistent anti-cyclonic circulation for 18 days in August, coincident with the most intense period of fire activity observed by Moderate Resolution Imaging Spectroradiometer (MODIS). This unfortunate meteorological coincidence allowed transport of polluted air from the region of intense fires to Moscow and the surrounding area. We demonstrate that the 2010 Russian wildfires are unique in the record of observations obtained by remote-sensing instruments on-board NASA satellites: Aura and Aqua (part of the A-Train Constellation) and Terra. Analysis of the distribution of MODIS fire products and aerosol optical thickness (AOT), UV aerosol index (AI) and single-scattering albedo (SSA) from Aura's Ozone Monitoring Instrument (OMI), and total column carbon monoxide (CO) from Aqua's Atmospheric Infrared Sounder (AIRS) show that the region in the center of western Russia surrounding Moscow (52°–58° N, 33°–43° E) is most severely impacted by wildfire emissions. Over this area, AIRS CO, OMI AI, and MODIS AOT are significantly enhanced relative to the historical satellite record during the first 18 days in August when the anti-cyclonic circulation persisted. By mid-August, the anti-cyclonic circulation was replaced with westerly transport over Moscow and vicinity. The heat wave ended as anomalies of surface temperature and relative humidity, and OLR disappeared. After 18 August the fire activity greatly diminished over western Russia and levels of the satellite smoke tracers returned to values typical of previous years.

We used the seasonality of a combination of atmospheric trace gases and idealized tracers to examine stratosphere-to-troposphere transport and its influence on tropospheric composition in the Arctic. Maximum stratosphere-to-troposphere transport of CFCs and O3 occurs in April as driven by the Brewer-Dobson circulation. Stratosphere-troposphere exchange (STE) occurs predominantly between 40° N to 80° N with stratospheric influx in the mid-latitudes (30–70° N) accounting for 67–81% of the air of stratospheric origin in the Northern Hemisphere extratropical troposphere. Transport from the lower stratosphere to the lower troposphere (LT) takes three months on average, one month to cross the tropopause, the second month to travel from the upper troposphere (UT) to the middle troposphere (MT), and the third month to reach the LT. During downward transport, the seasonality of a trace gas can be greatly impacted by wet removal and chemistry. A comparison of idealized tracers with varying lifetimes suggests that when initialized with the same concentrations and seasonal cycles at the tropopause, trace gases that have shorter lifetimes display lower concentrations, smaller amplitudes, and earlier seasonal maxima during transport to the LT. STE contributes to O3 in the Arctic troposphere directly from the transport of O3 and indirectly from the transport of NOy. Direct transport of O3 from the stratosphere accounts for 78% of O3 in the Arctic UT with maximum contributions occurring from March to May. The stratospheric contribution decreases significantly in the MT/LT (20–25% of total O3) and shows a very weak March–April maximum. Our NOx budget analysis in the Arctic UT shows that during spring and summer, the stratospheric injection of NOy-rich air increases NOx concentrations above the 20 pptv threshold level, thereby shifting the Arctic UT from a regime of net photochemical ozone loss to one of net production with rates as high as +16 ppbv/month.

This paper presents extensive {bias determination} analyses of ozone observations from the Atmospheric Chemistry Experiment (ACE) satellite instruments: the ACE Fourier Transform Spectrometer (ACE-FTS) and the Measurement of Aerosol Extinction in the Stratosphere and Troposphere Retrieved by Occultation (ACE-MAESTRO) instrument. Here we compare the latest ozone data products from ACE-FTS and ACE-MAESTRO with coincident observations from nearly 20 satellite-borne, airborne, balloon-borne and ground-based instruments, by analysing volume mixing ratio profiles and partial column densities. The ACE-FTS version 2.2 Ozone Update product reports more ozone than most correlative measurements from the upper troposphere to the lower mesosphere. At altitude levels from 16 to 44 km, the average values of the mean relative differences are nearly all within +1 to +8%. At higher altitudes (45–60 km), the ACE-FTS ozone amounts are significantly larger than those of the comparison instruments, with mean relative differences of up to +40% (about +20% on average). For the ACE-MAESTRO version 1.2 ozone data product, mean relative differences are within ±10% (average values within ±6%) between 18 and 40 km for both the sunrise and sunset measurements. At higher altitudes (~35–55 km), systematic biases of opposite sign are found between the ACE-MAESTRO sunrise and sunset observations. While ozone amounts derived from the ACE-MAESTRO sunrise occultation data are often smaller than the coincident observations (with mean relative differences down to −10%), the sunset occultation profiles for ACE-MAESTRO show results that are qualitatively similar to ACE-FTS, indicating a large positive bias (mean relative differences within +10 to +30%) in the 45–55 km altitude range. In contrast, there is no significant systematic difference in bias found for the ACE-FTS sunrise and sunset measurements.

During the INTEX-B (Intercontinental Chemical Transport Experiment)/ MILAGRO (Megacities Initiative: Local and Global Research Observations) experiments in March 2006 and the associated IONS-06 (INTEX Ozonesonde Network Study; http://croc.gsfc.nasa.gov/intexb/ions06.html), regular ozonesonde launches were made over 15 North American sites. The soundings were strategically positioned to study inter-regional flows and meteorological interactions with a mixture of tropospheric O3 sources: local pollution; O3 associated with convection and lightning; stratosphere-troposphere exchange. The variability of tropospheric O3 over the Mexico City Basin (MCB; 19° N, 99° W) and Houston (30° N, 95° W) is reported here. MCB and Houston profiles displayed a double tropopause in most soundings and a subtropical tropopause layer with frequent wave disturbances, identified through O3 laminae as gravity-wave induced. Ozonesondes launched over both cities in August and September 2006 (IONS-06, Phase 3) displayed a thicker tropospheric column O3 (~7 DU or 15–20%) than in March 2006; nearly all of the increase was in the free troposphere. In spring and summer, O3 laminar structure manifested mixed influences from the stratosphere, convective redistribution of O3 and precursors, and O3 from lightning NO. Stratospheric O3 origins were present in 39% (MCB) and 60% (Houston) of the summer sondes. Comparison of summer 2006 O3 structure with summer 2004 sondes (IONS-04) over Houston showed 7% less tropospheric O3 in 2006. This may reflect a sampling contrast, August to mid-September 2006 instead of July-mid August 2004.

We examine the tropical ozone mixing ratio perturbation fields generated from a monthly ozone climatology using 1998 to 2006 ozonesonde data from the Southern Hemisphere Additional Ozonesondes (SHADOZ) network and the 13-year satellite record from 1993 to 2005 obtained from the Halogen Occultation Experiment (HALOE). The long time series and high vertical resolution of the ozone and temperature profiles from the SHADOZ sondes coupled with good tropical coverage north and south of the equator gives a detailed picture of the ozone structure in the lowermost stratosphere down through the tropopause where the picture obtained from HALOE measurements is blurred by coarse vertical resolution. Ozone perturbations respond to annual variations in the Brewer-Dobson Circulation (BDC) in the region just above the cold-point tropopause to around 20 km. Annual cycles in ozone and temperature are well correlated. Above 20 km, ozone and temperature perturbations are dominated by the Quasi-biennial Oscillation (QBO). Both satellite and sonde records show good agreement between positive and negative ozone mixing ratio anomalies and alternating QBO westerly and easterly wind shears from the Singapore rawinsondes with a mean periodicity of 26 months for SHADOZ and 25 months for HALOE. There is a temporal offset of one to three months with the QBO wind shear ahead of the ozone anomaly field. The meridional length scales for the annual cycle and the QBO, obtained using the temperature anomalies and wind shears in the thermal wind equation, compare well with theoretical calculations.