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While the Montreal Protocol is reducing stratospheric ozone loss, recent increases in some ozone depleting substance (ODS) emissions have been identified that may impact southern hemisphere climate systems. In this study, we discuss characteristics of the 2018 and 2019 Antarctic ozone holes using surface in situ, satellite and reanalysis data to gain a better understanding of recent ozone variability. These ozone holes had strongly contrasting characteristics. In 2018, the Antarctic stratospheric vortex was relatively stable and cold in comparison to most years of the prior decade. This resulted in a large and persistent ozone hole that ranked in the upper-tercile of metrics quantifying Antarctic ozone depletion. In contrast, strong stratospheric warming in the spring of 2019 curtailed the development of the ozone hole, causing it to be anomalously small and of similar size to ozone holes in the 1980s. As known from previous studies, the ability of planetary waves to propagate into the stratosphere at high latitudes is an important factor that influences temperatures of the polar vortex and the overall amount of ozone loss in any particular year. Disturbance and warming of the vortex by strong planetary wave activity were the dominant factors in the small 2019 ozone hole. In contrast, planetary wave disturbances to the vortex in the winter–spring of 2018 were much weaker than in 2019. These results increase our understanding of the impact of Montreal Protocol controls on ODS and the effects of Antarctic ozone on the southern hemisphere climate system.

Carbonyl sulfide (OCS) is a non-hygroscopic trace species in the free troposphere and the primary sulfur reservoir maintained by direct oceanic, geologic, biogenic and anthropogenic emissions and t...

Using multidecadal time series of ground-based and satellite Fourier transform infrared measurements of inorganic fluorine (i.e., total fluorine resident in stratospheric fluorine reservoirs), we investigate stratospheric circulation changes over the past 20 years. The representation of these changes in five modern reanalyses is further analyzed through chemical-transport model (CTM) simulations. From the observations but also from all reanalyses, we show that the inorganic fluorine is accumulating less rapidly in the Southern Hemisphere than in the Northern Hemisphere during the 21st century. Comparisons with a study evaluating the age-of-air of these reanalyses using the same CTM allow us to link this hemispheric asymmetry to changes in the Brewer-Dobson circulation (BDC), with the age-of-air of the Southern Hemisphere getting younger relative to that of the Northern Hemisphere. Large differences in simulated total columns and absolute trend values are, nevertheless, depicted between our simulations driven by the five reanalyses. Superimposed on this multidecadal change, we, furthermore, confirm a 5–7-year variability of the BDC that was first described in a recent study analyzing long-term time series of hydrogen chloride (HCl) and nitric acid (HNO3). It is important to stress that our results, based on observations and meteorological reanalyses, are in contrast with the projections of chemistry-climate models in response to the coupled increase of greenhouse gases and decrease of ozone-depleting substances, calling for further investigations and the continuation of long-term observations.

Atmospheric observations of CO2 and other greenhouse gases have been widely used to constrain estimates of terrestrial and oceanic CO2 fluxes through atmospheric inverse modelling. Yet, applying these methods at national scale to verify and improve the National Inventory Report (NIR) and support the Paris agreement remains at the frontier of CO2 science.We use inverse modelling to estimate New Zealand’s carbon uptake and emissions using atmospheric measurements and model. This effort is part of a five year CarbonWatch-NZ research programme, which aims to develop a complete top-down picture of New Zealand's carbon balance using national inverse modelling and targeted studies of New Zealand’s forest, grassland and urban environments. In addition to quantifying New Zealand’s carbon emissions on a national scale, we also focus on identifying the prevailing processes driving CO2 changes in New Zealand to support climate mitigation.In an initial study based on the inversion system used in CarbonWatch-NZ, a significantly stronger (30-60 %) sink was found relative to the NIR (Steinkamp et al., 2017), suggesting a strong CO2 uptake in Fiordland, a region covered by indigenous temperate rainforest in New Zealand's South Island. Here, we present new results of CarbonWatch-NZ by expanding the studied time period from 2011-2013 to 2020, expanding our atmospheric observing network from two (Baring Head, 41.41°S, 174.87°E and Lauder, 38.33°S, 176.38°E) to a total of eleven in situ greenhouse gas measurement sites and improving our atmospheric model resolution by roughly a factor of ten (NAME model, 1.5 km).Our new results suggest that the strong sink observed in 2011-2013 did not diminish, but for recent years we have found an even stronger sink than for before. Additional measurements collected in the Fiordland region (i.e., mixing ratios, CO2 isotopes, carbonyl sulphide) also suggest a stronger CO2 uptake, supporting our inversion results. Both the measurements and inversion results show that the CO2 uptake does not seem to shut down completely during winter time, suggesting that there might be something about this ecosystem that we do not yet understand. This winter uptake signal is also present in independent data collected in and around New Zealand as part of the ATom campaigns (Atmospheric Tomography Mission). Implementing observations from an additional site in the North Island (Maunga Kakaramea, 45.034°S, 169.68°E) has increased the strength of the sink, pointing to additional strong sink region at the top of the North Island. ReferencesKay Steinkamp, Sara E. Mikaloff Fletcher, Gordon Brailsford, Dan Smale, Stuart Moore, Elizabeth D. Keller, W. Troy Baisden, Hitoshi Mukai and Britton B. Stephens, Atmospheric CO2 observations and models suggest strong carbon uptake by forests in New Zealand, Atmospheric Chemistry and Physics, 2017.

We review the 2017 Antarctic ozone hole, making use of various meteorological reanalyses, and in-situ, satellite and ground-based measurements of ozone and related trace gases, and ground-based measurements of ultraviolet radiation. The 2017 ozone hole was associated with relatively high-ozone concentrations over the Antarctic region compared to other years, and our analysis ranked it in the smallest 25% of observed ozone holes in terms of size. The severity of stratospheric ozone loss was comparable with that which occurred in 2002 (when the stratospheric vortex exhibited an unprecedented major warming) and most years prior to 1989 (which were early in the development of the ozone hole). Disturbances to the polar vortex in August and September that were associated with intervals of anomalous planetary wave activity resulted in significant erosion of the polar vortex and the mitigation of the overall level of ozone depletion. The enhanced wave activity was favoured by below-average westerly winds at high southern latitudes during winter, and the prevailing easterly phase of the quasi-biennial oscillation (QBO). Using proxy information on the chemical make-up of the polar vortex based on the analysis of nitrous oxide and the likely influence of the QBO, we suggest that the concentration of inorganic chlorine, which plays a key role in ozone loss, was likely similar to that in 2014 and 2016, when the ozone hole was larger than that in 2017. Finally, we found that the overall severity of Antarctic ozone loss in 2017 was largely dictated by the timing of the disturbances to the polar vortex rather than interannual variability in the level of inorganic chlorine.

Man-made halogenated compounds emitted from the Earth’s surface ultimately reach the stratosphere where they undergo photolysis, leading to three main fluorine reservoirs: hydrogen fluoride (HF), carbonyl fluoride (COF2) and carbonyl chloride fluoride (COClF). This process is directly influenced by the strength of the mean meridional circulation of the stratosphere, the Brewer-Dobson Circulation (BDC). The BDC is projected to speed-up with the greenhouse gases induced global warming. However, studies have highlighted a multiyear variability in the strength of the BDC resulting in hemispheric asymmetries in observed and modelled trends of age of air and long-lived tracers.Total inorganic fluorine (Fy, the fluorine weighted sum of HF, COF2 and COClF) is used here as a tracer of the stratospheric circulation changes. We perform an analysis and interpretation of Fourier transform infrared (FTIR) multidecadal time-series of HF and COF2 from the Jungfraujoch (Switzerland, 46.55°N) and Lauder (New-Zealand, 45.03°S) stations and from the space-borne Atmospheric Chemistry Experiment - Fourier Transform Spectrometer (ACE-FTS). Indeed, the summation of HF and COF2 is a very good proxy of Fy as we determine, from ACE-FTS and the chemical-transport model (CTM) TOMCAT, that COClF is only accounting for less than 5% of the total Fy budget.The kinematic CTM BASCOE (Belgian assimilation system for chemical observations) is used here to assess the representation of the investigated circulation changes in four state-of-the-art meteorological reanalyses, i.e., ERA-Interim, JRA-55, MERRA and MERRA-2. We also investigate if WACCM4 (Whole Atmosphere Community Climate Model version 4) is able to reproduce these changes through a free-running simulation.The ground-based and satellite FTIR time-series of COF2 show contrasting results over their common time period (2004-2019), with a positive total column trend above the Jungfraujoch, and a non-significant (ground-based) or decreasing trend (ACE-FTS) above Lauder. We find large discrepancies between the BASCOE-CTM simulations, with MERRA-2 inducing overly large simulated Fy total columns which could confirm the weaker tropical upwelling highlighted in previous age of air studies.

TROPOMI (the TROPOspheric Monitoring Instrument), on-board the Sentinel-5 Precursor satellite, has been monitoring the Earth's atmosphere since October 2017, with an unprecedented horizontal resolution (initially 7×3.5 km2, upgraded to 5.5×3.5 km2 since August 2019). Monitoring air quality is one of the main objectives of TROPOMI, with the measurements of important pollutants such as nitrogen dioxide, carbon monoxide, and formaldehyde (HCHO). In this paper we assess the quality of the latest HCHO TROPOMI products (version 1.1.[5-7]), using ground-based solar-absorption FTIR (Fourier Transform Infrared) measurements of HCHO from twenty-five stations around the world, including high, mid, and low latitude sites. Most of these stations are part of the Network for the Detection of Atmospheric Composition Change (NDACC), and they provide a wide range of observation conditions from very clean remote sites to those with high HCHO levels from anthropogenic or biogenic emissions. The ground-based HCHO retrieval settings have been optimized and harmonized at all the stations, ensuring a consistent validation among the sites. In this validation work, we first assess the accuracy of TROPOMI HCHO tropospheric columns, using the median of the relative differences between TROPOMI and FTIR ground-based data (BIAS). We observe that, at all sites, the TROPOMI accuracy is below the upper limit of the pre-launch requirements of 80 %, and below the lower limit of 40 % for 20 of the 25 stations. The provided TROPOMI systematic uncertainties are well in agreement with the observed biases at most of the stations, except for the highest HCHO levels site where it is found to be underestimated. We find that, while the BIAS has no latitudinal dependence, it is dependent on the HCHO concentration levels: an overestimation (+26 ± 5 %) of TROPOMI is observed for very small HCHO levels ( 8.0 × 1015 molec/cm2). This demonstrates the great value of such a harmonized network covering a wide range of concentration levels, the sites with high HCHO concentrations being crucial for the determination of the satellite bias at the regions of emissions, and the clean sites allowing a small TROPOMI offset to be determined. The wide range of sampled HCHO levels within the network allows the robust determination of the significant constant and proportional TROPOMI HCHO biases (TROPOMI=+ 1.10 (± 0.05) × 1015+ 0.64 (± 0.03) × FTIR, in molec/cm2). Second, the precision of TROPOMI HCHO data is estimated by the median absolute deviation (MAD) of the relative differences between TROPOMI and FTIR ground-based data. The clean sites are especially useful to minimize a possible additional collocation error. The precision requirement of 1.2 × 1016 molec/cm2 for a single pixel is reached at most of the clean sites, where it is found that the TROPOMI precision can even be twice better (0.5–0.8 × 1015 molec/cm2 for a single pixel). However, we find that the provided TROPOMI random uncertainties may be underestimated by a factor of 1.6 (for clean sites) to 2.3 (for high HCHO levels). The correlation is very good between TROPOMI and FTIR data (R = 0.88 for 3 hours-mean coincidences; R = 0.91 for monthly means coincidences). Using about 17 months of data (from May 2018 to September 2019), we show that the TROPOMI seasonal variability is in very good agreement at all of the FTIR sites. The FTIR network demonstrates the very good quality of the TROPOMI HCHO products which is well within the pre-launch requirements for both accuracy and precision. This paper advises for a refinement of the TROPOMI random uncertainty budget and of the TROPOMI quality assurance values for a better filtering of the remaining outliers.

TROPOMI (the TROPOspheric Monitoring Instrument), on board the Sentinel-5 Precursor (S5P) satellite, has been monitoring the Earth's atmosphere since October 2017 with an unprecedented horizontal resolution (initially 7 km2×3.5 km2, upgraded to 5.5 km2×3.5 km2 in August 2019). Monitoring air quality is one of the main objectives of TROPOMI; it obtains measurements of important pollutants such as nitrogen dioxide, carbon monoxide, and formaldehyde (HCHO). In this paper we assess the quality of the latest HCHO TROPOMI products versions 1.1.(5-7), using ground-based solar-absorption FTIR (Fourier-transform infrared) measurements of HCHO from 25 stations around the world, including high-, mid-, and low-latitude sites. Most of these stations are part of the Network for the Detection of Atmospheric Composition Change (NDACC), and they provide a wide range of observation conditions, from very clean remote sites to those with high HCHO levels from anthropogenic or biogenic emissions. The ground-based HCHO retrieval settings have been optimized and harmonized at all the stations, ensuring a consistent validation among the sites. In this validation work, we first assess the accuracy of TROPOMI HCHO tropospheric columns using the median of the relative differences between TROPOMI and FTIR ground-based data (BIAS). The pre-launch accuracy requirements of TROPOMI HCHO are 40 %–80 %. We observe that these requirements are well reached, with the BIAS found below 80 % at all the sites and below 40 % at 20 of the 25 sites. The provided TROPOMI systematic uncertainties are well in agreement with the observed biases at most of the stations except for the highest-HCHO-level site, where it is found to be underestimated. We find that while the BIAS has no latitudinal dependence, it is dependent on the HCHO concentration levels: an overestimation (+26±5 %) of TROPOMI is observed for very low HCHO levels (<2.5×1015 molec. cm−2), while an underestimation (-30.8%±1.4 %) is found for high HCHO levels (>8.0×1015 molec. cm−2). This demonstrates the great value of such a harmonized network covering a wide range of concentration levels, the sites with high HCHO concentrations being crucial for the determination of the satellite bias in the regions of emissions and the clean sites allowing a small TROPOMI offset to be determined. The wide range of sampled HCHO levels within the network allows the robust determination of the significant constant and proportional TROPOMI HCHO biases (TROPOMI =+1.10±0.05 ×1015+0.64±0.03 × FTIR; in molecules per square centimetre). Second, the precision of TROPOMI HCHO data is estimated by the median absolute deviation (MAD) of the relative differences between TROPOMI and FTIR ground-based data. The clean sites are especially useful for minimizing a possible additional collocation error. The precision requirement of 1.2×1016 molec. cm−2 for a single pixel is reached at most of the clean sites, where it is found that the TROPOMI precision can even be 2 times better (0.5–0.8×1015 molec. cm−2 for a single pixel). However, we find that the provided TROPOMI random uncertainties may be underestimated by a factor of 1.6 (for clean sites) to 2.3 (for high HCHO levels). The correlation is very good between TROPOMI and FTIR data (R=0.88 for 3 h mean coincidences; R=0.91 for monthly means coincidences). Using about 17 months of data (from May 2018 to September 2019), we show that the TROPOMI seasonal variability is in very good agreement at all of the FTIR sites. The FTIR network demonstrates the very good quality of the TROPOMI HCHO products, which is well within the pre-launch requirements for both accuracy and precision. This paper makes suggestions for the refinement of the TROPOMI random uncertainty budget and TROPOMI quality assurance values for a better filtering of the remaining outliers.

The El Niño–Southern Oscillation (ENSO) has been suggested as a strong forcing in the methane cycle and as a driver of recent trends in global atmospheric methane mole fractions [CH4]. Such a sensitivity of the global CH4 budget to climate events would have important repercussions for climate change mitigation strategies and the accuracy of projections for future greenhouse forcing. Here, we test the impact of ENSO on atmospheric CH4 in a correlation analysis. We use local and global records of [CH4], as well as stable carbon isotopic records of atmospheric CH4 (δ13CH4), which are particularly sensitive to the combined ENSO effects on CH4 production from wetlands and biomass burning. We use a variety of nominal, smoothed, and detrended time series including growth rate records. We find that at most 36 % of the variability in [CH4] and δ13CH4 is attributable to ENSO, but only for detrended records in the southern tropics. Trend-bearing records from the southern tropics, as well as all studied hemispheric and global records, show a minor impact of ENSO, i.e. CH4 production that responds less to ENSO than previously suggested. Dynamics of the removal by hydroxyl likely counteract the variation in emissions, but the expected isotope signal is not evident. It is possible that other processes obscure the ENSO signal, which itself indicates a minor influence of the latter on global CH4 emissions. Trends like the recent rise in atmospheric [CH4] can therefore not be attributed to ENSO. This leaves anthropogenic methane sources as the likely driver, which must be mitigated to reduce anthropogenic climate change.

Among the more than 20 ground-based FTIR (Fourier transform infrared) stations currently operating around the globe, only a few have provided formaldehyde (HCHO) total column time series until now. Although several independent studies have shown that the FTIR measurements can provide formaldehyde total columns with good precision, the spatial coverage has not been optimal for providing good diagnostics for satellite or model validation. Furthermore, these past studies used different retrieval settings, and biases as large as 50 % can be observed in the HCHO total columns depending on these retrieval choices, which is also a weakness for validation studies combining data from different ground-based stations.For the present work, the HCHO retrieval settings have been optimized based on experience gained from past studies and have been applied consistently at the 21 participating stations. Most of them are either part of the Network for the Detection of Atmospheric Composition Change (NDACC) or under consideration for membership. We provide the harmonized settings and a characterization of the HCHO FTIR products. Depending on the station, the total systematic and random uncertainties of an individual HCHO total column measurement lie between 12 % and 27 % and between 1 and 11×1014 molec cm−2, respectively. The median values among all stations are 13 % and 2.9×1014 molec cm−2 for the total systematic and random uncertainties.This unprecedented harmonized formaldehyde data set from 21 ground-based FTIR stations is presented and its comparison with a global chemistry transport model shows consistency in absolute values as well as in seasonal cycles. The network covers very different concentration levels of formaldehyde, from very clean levels at the limit of detection (few 1013 molec cm−2) to highly polluted levels (7×1016 molec cm−2). Because the measurements can be made at any time during daylight, the diurnal cycle can be observed and is found to be significant at many stations. These HCHO time series, some of them starting in the 1990s, are crucial for past and present satellite validation and will be extended in the coming years for the next generation of satellite missions.

We report on the ground-based FTIR (Fourier transform infrared) tropospheric water vapour isotopologue remote sensing data that have been recently made available via the database of NDACC (Network for the Detection of Atmospheric Composition Change; ftp://ftp.cpc.ncep.noaa.gov/ndacc/MUSICA/) and via doi:10.5281/zenodo.48902. Currently, data are available for 12 globally distributed stations. They have been centrally retrieved and quality-filtered in the framework of the MUSICA project (MUlti-platform remote Sensing of Isotopologues for investigating the Cycle of Atmospheric water). We explain particularities of retrieving the water vapour isotopologue state (vertical distribution of H216O, H218O, and HD16O) and reveal the need for a new metadata template for archiving FTIR isotopologue data. We describe the format of different data components and give recommendations for correct data usage. Data are provided as two data types. The first type is best-suited for tropospheric water vapour distribution studies disregarding different isotopologues (comparison with radiosonde data, analyses of water vapour variability and trends, etc.). The second type is needed for analysing moisture pathways by means of H2O, δD-pair distributions.

Nitrous oxide (N2O) is an important greenhouse gas and it can also generate nitric oxide, which depletes ozone in the stratosphere. It is a common target species of ground-based Fourier transform infrared (FTIR) near-infrared (TCCON) and mid-infrared (NDACC) measurements. Both TCCON and NDACC networks provide a long-term global distribution of atmospheric N2O mole fraction. In this study, the dry-air column-averaged mole fractions of N2O (XN2O) from the TCCON and NDACC measurements are compared against each other at seven sites around the world (Ny-Ålesund, Sodankylä, Bremen, Izaña, Réunion, Wollongong, Lauder) in the time period of 2007–2017. The mean differences in XN2O between TCCON and NDACC (NDACC–TCCON) at these sites are between −3.32 and 1.37 ppb (−1.1 %–0.5 %) with standard deviations between 1.69 and 5.01 ppb (0.5 %–1.6 %), which are within the uncertainties of the two datasets. The NDACC N2O retrieval has good sensitivity throughout the troposphere and stratosphere, while the TCCON retrieval underestimates a deviation from the a priori in the troposphere and overestimates it in the stratosphere. As a result, the TCCON XN2O measurement is strongly affected by its a priori profile. Trends and seasonal cycles of XN2O are derived from the TCCON and NDACC measurements and the nearby surface flask sample measurements and compared with the results from GEOS-Chem model a priori and a posteriori simulations. The trends and seasonal cycles from FTIR measurement at Ny-Ålesund and Sodankylä are strongly affected by the polar winter and the polar vortex. The a posteriori N2O fluxes in the model are optimized based on surface N2O measurements with a 4D-Var inversion method. The XN2O trends from the GEOS-Chem a posteriori simulation (0.97±0.02 (1σ) ppb yr−1) are close to those from the NDACC (0.93±0.04 ppb yr−1) and the surface flask sample measurements (0.93±0.02 ppb yr−1). The XN2O trend from the TCCON measurements is slightly lower (0.81±0.04 ppb yr−1) due to the underestimation of the trend in TCCON a priori simulation. The XN2O trends from the GEOS-Chem a priori simulation are about 1.25 ppb yr−1, and our study confirms that the N2O fluxes from the a priori inventories are overestimated. The seasonal cycles of XN2O from the FTIR measurements and the model simulations are close to each other in the Northern Hemisphere with a maximum in August–October and a minimum in February–April. However, in the Southern Hemisphere, the modeled XN2O values show a minimum in February–April while the FTIR XN2O retrievals show different patterns. By comparing the partial column-averaged N2O from the model and NDACC for three vertical ranges (surface–8, 8–17, 17–50 km), we find that the discrepancy in the XN2O seasonal cycle between the model simulations and the FTIR measurements in the Southern Hemisphere is mainly due to their stratospheric differences.

We use ground-based spectroscopic remote sensing measurements of the stratospheric trace gases O3, HCl, ClO, BrO, HNO3, NO2, OClO, ClONO2, N2O and HF, along with radiosonde profiles of temperature ...

Atmospheric non-methane hydrocarbon concentrations began declining in the 1970s. Surface and column measurements show that Northern Hemisphere ethane concentrations are now rising, probably due to North American oil and natural gas emissions. Non-methane hydrocarbons such as ethane are important precursors to tropospheric ozone and aerosols. Using data from a global surface network and atmospheric column observations we show that the steady decline in the ethane mole fraction that began in the 1970s1,2,3 halted between 2005 and 2010 in most of the Northern Hemisphere and has since reversed. We calculate a yearly increase in ethane emissions in the Northern Hemisphere of 0.42 (±0.19) Tg yr−1 between mid-2009 and mid-2014. The largest increases in ethane and the shorter-lived propane are seen over the central and eastern USA, with a spatial distribution that suggests North American oil and natural gas development as the primary source of increasing emissions. By including other co-emitted oil and natural gas non-methane hydrocarbons, we estimate a Northern Hemisphere total non-methane hydrocarbon yearly emission increase of 1.2 (±0.8) Tg yr−1. Atmospheric chemical transport modelling suggests that these emissions could augment summertime mean surface ozone by several nanomoles per mole near oil and natural gas production regions. Methane/ethane oil and natural gas emission ratios could suggest a significant increase in associated methane emissions; however, this increase is inconsistent with observed leak rates in production regions and changes in methane’s global isotopic ratio.

The El Nino – Southern Oscillation (ENSO) has been suggested as a strong forcing in the methane cycle and as a driver of recent trends in global atmospheric methane levels. Such a sensitivity of the global CH 4 budget to climate events would have important repercussions for climate change mitigation strategies and the accuracy of projections for future greenhouse forcing. Here, we test the impact of ENSO on the CH 4 cycle in a correlation analysis. We use local and global records of methane mixing ratio [CH 4 ], as well as stable carbon isotopic records of atmospheric CH 4 (δ 13 CH 4 ), which are particularly sensitive to the combined ENSO effects on CH 4 production from wetlands and biomass burning. We use a variety of nominal, smoothed and detrended time series including growth rate records. We find that at most 38 % of the variability in [CH 4 ] and δ 13 CH 4 is attributable to ENSO, but only for detrended records in the Southern tropics. Trend-bearing records from the Southern tropics, as well as all studied hemispheric and global records show a minor impact of ENSO, i.e. 25 % of variability explained. Additional analyses using hydrogen cyanide (HCN) records show a detectable ENSO influence on biomass burning (up to 51 %–55 %), suggesting that it is wetland CH 4 production that responds less to ENSO than previously suggested. It is possible that other processes obscure the ENSO signal, which itself indicates a minor influence of the latter on CH 4 emissions. Trends like the recent rise in atmospheric [CH 4 ] can therefore not be attributed to ENSO. This leaves anthropogenic methane sources as the likely driver, which must be mitigated to reduce anthropogenic climate change.

Transport of carbonyl sulfide (OCS) from the troposphere to the stratosphere contributes sulfur to the stratospheric aerosol layer, which reflects incoming short-wave solar radiation, cooling the climate system. Previous analyses of OCS observations have shown no significant trend, suggesting that OCS is unlikely to be a major contributor to the reported increases in stratospheric aerosol loading and indicating a balanced OCS budget. Here we present analyses of ground-based Fourier transform spectrometer measurements of OCS at three Southern Hemisphere sites spanning 34.45°S to 77.80°S. At all three sites statistically significant positive trends are seen from 2001 to 2014 with an observed overall trend in total column OCS at Wollongong of 0.73 ± 0.03%/yr, at Lauder of 0.43 ± 0.02%/yr, and at Arrival Heights of 0.45 ± 0.05%/yr. These observed trends in OCS imply that the OCS budget is not balanced and could contribute to constraints on current estimates of sources and sinks.

We investigate the impact of biogenic emissions on carbon monoxide (CO) and formaldehyde (HCHO) in the Southern Hemisphere (SH), with simulations using two different biogenic emission inventories for isoprene and monoterpenes. Results from four atmospheric chemistry models are compared to continuous long-term ground-based CO and HCHO column measurements at the SH Network for the Detection of Atmospheric Composition Change (NDACC) sites, the satellite measurement of tropospheric CO columns from the Measurement of Pollution in the Troposphere (MOPITT), and in situ surface CO measurements from across the SH, representing a subset of the National Oceanic and Atmospheric Administration's Global Monitoring Division (NOAA GMD) network. Simulated mean model CO using the Model of Emissions of Gases and Aerosols from Nature (v2.1) computed in the frame work of the Land Community Model (CLM-MEGANv2.1) inventory is in better agreement with both column and surface observations than simulations adopting the emission inventory generated from the LPJ-GUESS dynamical vegetation model framework, which markedly underestimate measured column and surface CO at most sites. Differences in biogenic emissions cause large differences in CO in the source regions which propagate to the remote SH. Significant inter-model differences exist in modelled column and surface CO, and secondary production of CO dominates these inter-model differences, due mainly to differences in the models' oxidation schemes for volatile organic compounds, predominantly isoprene oxidation. While biogenic emissions are a significant factor in modelling SH CO, inter-model differences pose an additional challenge to constrain these emissions. Corresponding comparisons of HCHO columns at two SH mid-latitude sites reveal that all models significantly underestimate the observed values by approximately a factor of 2. There is a much smaller impact on HCHO of the significantly different biogenic emissions in remote regions, compared to the source regions. Decreased biogenic emissions cause decreased CO export to remote regions, which leads to increased OH; this in turn results in increased HCHO production through methane oxidation. In agreement with earlier studies, we corroborate that significant HCHO sources are likely missing in the models in the remote SH.

Ground-based Fourier transform infrared (FTIR) measurements of solar absorption spectra can provide ozone total columns with a precision of 2% but also independent partial column amounts in about four vertical layers, one in the troposphere and three in the stratosphere up to about 45km, with a precision of 5–6%. We use eight of the Network for the Detection of Atmospheric Composition Change (NDACC) stations having a long-term time series of FTIR ozone measurements to study the total and vertical ozone trends and variability, namely, Ny-Ålesund (79° N), Thule (77° N), Kiruna (68° N), Harestua (60° N), Jungfraujoch (47° N), Izaña (28° N), Wollongong (34° S) and Lauder (45° S). The length of the FTIR time series varies by station but is typically from about 1995 to present. We applied to the monthly means of the ozone total and four partial columns a stepwise multiple regression model including the following proxies: solar cycle, quasi-biennial oscillation (QBO), El Niño–Southern Oscillation (ENSO), Arctic and Antarctic Oscillation (AO/AAO), tropopause pressure (TP), equivalent latitude (EL), Eliassen–Palm flux (EPF), and volume of polar stratospheric clouds (VPSC). At the Arctic stations, the trends are found mostly negative in the troposphere and lower stratosphere, very mixed in the middle stratosphere, positive in the upper stratosphere due to a large increase in the 1995–2003 period, and non-significant when considering the total columns. The trends for mid-latitude and subtropical stations are all non-significant, except at Lauder in the troposphere and upper stratosphere and at Wollongong for the total columns and the lower and middle stratospheric columns where they are found positive. At Jungfraujoch, the upper stratospheric trend is close to significance (+0.9 ± 1.0% decade−1). Therefore, some signs of the onset of ozone mid-latitude recovery are observed only in the Southern Hemisphere, while a few more years seem to be needed to observe it at the northern mid-latitude station.

The abundance of chlorine in the Earth's atmosphere increased considerably during the 1970s to 1990s, following large emissions of anthropogenic long-lived chlorine-containing source gases, notably the chlorofluorocarbons. The chemical inertness of chlorofluorocarbons allows their transport and mixing throughout the troposphere on a global scale, before they reach the stratosphere where they release chlorine atoms that cause ozone depletion. The large ozone loss over Antarctica was the key observation that stimulated the definition and signing in 1987 of the Montreal Protocol, an international treaty establishing a schedule to reduce the production of the major chlorine- and bromine-containing halocarbons. Owing to its implementation, the near-surface total chlorine concentration showed a maximum in 1993, followed by a decrease of half a per cent to one per cent per year, in line with expectations. Remote-sensing data have revealed a peak in stratospheric chlorine after 1996, then a decrease of close to one per cent per year, in agreement with the surface observations of the chlorine source gases and model calculations. Here we present ground-based and satellite data that show a recent and significant increase, at the 2σ level, in hydrogen chloride (HCl), the main stratospheric chlorine reservoir, starting around 2007 in the lower stratosphere of the Northern Hemisphere, in contrast with the ongoing monotonic decrease of near-surface source gases. Using model simulations, we attribute this trend anomaly to a slowdown in the Northern Hemisphere atmospheric circulation, occurring over several consecutive years, transporting more aged air to the lower stratosphere, and characterized by a larger relative conversion of source gases to HCl. This short-term dynamical variability will also affect other stratospheric tracers and needs to be accounted for when studying the evolution of the stratospheric ozone layer.

Chemistry-climate models (CCMs) project an earlier return of northern mid-latitude total column ozone to 1980 values compared to the southern mid-latitudes. The chemical and dynamical drivers of this hemispheric difference are investigated in this study. The hemispheric asymmetry in return dates is a robust result across different CCMs and is qualitatively independent of the method used to estimate return dates. However, the differences in dates of return to 1980 levels between the southern and northern mid-latitudes can vary between 0 and 30 yr across the range of CCM projections analyzed. Positive linear trends in ozone lead to an earlier return of ozone than expected from the return of Cly to 1980 levels. This forward shift is stronger in the Northern than in the Southern Hemisphere because (i) trends have a larger effect on return dates if the sensitivity of ozone to Cly is lower and (ii) the trends in the Northern Hemisphere are stronger than in the Southern Hemisphere. An attribution analysis performed with two CCMs shows that chemically-induced changes in ozone are the major driver of the earlier return of ozone to 1980 levels in northern mid-latitudes; therefore transport changes are of minor importance. This conclusion is supported by the fact that the spread in the simulated hemispheric difference in return dates across an ensemble of twelve models is only weakly related to the spread in the simulated hemispheric asymmetry of trends in the strength of the Brewer–Dobson circulation. The causes for chemically-induced asymmetric ozone trends relevant for the total column ozone return date differences are found to be (i) stronger increases in ozone production due to enhanced NOx concentrations in the Northern Hemisphere lowermost stratosphere and troposphere, (ii) stronger decreases in the destruction rates of ozone by the NOx cycle in the Northern Hemisphere lower stratosphere linked to effects of dynamics and temperature on NOx concentrations, and (iii) an increasing efficiency of heterogeneous ozone destruction by Cly in the Southern Hemisphere mid-latitudes as a~result of decreasing lower stratospheric temperatures.

Changes of atmospheric methane (CH4) since 2005 have been evaluated using Fourier Transform Infrared (FTIR) solar observations performed at ten ground-based sites, all members of the Network for Detection of Atmospheric Composition Change (NDACC). From this, we find an increase of atmospheric methane total columns that amounts to 0.31 ± 0.03 % year−1 (2-sigma level of uncertainty) for the 2005–2014 period. Comparisons with in situ methane measurements at both local and global scales show good agreement. We used the GEOS-Chem Chemical Transport Model tagged simulation that accounts for the contribution of each emission source and one sink in the total methane, simulated over the 2005–2012 time period and based on emissions inventories and transport. After regridding according to NDACC vertical layering using a conservative regridding scheme and smoothing by convolving with respective FTIR seasonal averaging kernels, the GEOS-Chem simulation shows an increase of atmospheric methane of 0.35 ± 0.03 % year−1 between 2005 and 2012, which is in agreement with NDACC measurements over the same time period (0.30 ± 0.04 % year−1, averaged over ten stations). Analysis of the GEOS-Chem tagged simulation allows us to quantify the contribution of each tracer to the global methane change since 2005. We find that natural sources such as wetlands and biomass burning contribute to the inter-annual variability of methane. However, anthropogenic emissions such as coal mining, and gas and oil transport and exploration, which are mainly emitted in the Northern Hemisphere and act as secondary contributors to the global budget of methane, have played a major role in the increase of atmospheric methane observed since 2005. Based on the GEOS-Chem tagged simulation, we discuss possible cause(s) for the increase of methane since 2005, which is still unexplained.

Time series of total column abundances of hydrogen chloride (HCl), chlorine nitrate (ClONO2), and hydrogen fluoride (HF) were determined from ground-based Fourier transform infrared (FTIR) spectra recorded at 17 sites belonging to the Network for the Detection of Atmospheric Composition Change (NDACC) and located between 80.05° N and 77.82° S. By providing such a near-global overview on ground-based measurements of the two major stratospheric chlorine reservoir species, HCl and ClONO2, the present study is able to confirm the decrease of the atmospheric inorganic chlorine abundance during the last few years. This decrease is expected following the 1987 Montreal Protocol and its amendments and adjustments, where restrictions and a subsequent phase-out of the prominent anthropogenic chlorine source gases (solvents, chlorofluorocarbons) were agreed upon to enable a stabilisation and recovery of the stratospheric ozone layer. The atmospheric fluorine content is expected to be influenced by the Montreal Protocol, too, because most of the banned anthropogenic gases also represent important fluorine sources. But many of the substitutes to the banned gases also contain fluorine so that the HF total column abundance is expected to have continued to increase during the last few years. The measurements are compared with calculations from five different models: the two-dimensional Bremen model, the two chemistry-transport models KASIMA and SLIMCAT, and the two chemistry-climate models EMAC and SOCOL. Thereby, the ability of the models to reproduce the absolute total column amounts, the seasonal cycles, and the temporal evolution found in the FTIR measurements is investigated and inter-compared. This is especially interesting because the models have different architectures. The overall agreement between the measurements and models for the total column abundances and the seasonal cycles is good. Linear trends of HCl, ClONO2, and HF are calculated from both measurement and model time series data, with a focus on the time range 2000–2009. This period is chosen because from most of the measurement sites taking part in this study, data are available during these years. The precision of the trends is estimated with the bootstrap resampling method. The sensitivity of the trend results with respect to the fitting function, the time of year chosen and time series length is investigated, as well as a bias due to the irregular sampling of the measurements. The measurements and model results investigated here agree qualitatively on a decrease of the chlorine species by around 1% yr−1. The models simulate an increase of HF of around 1% yr−1. This also agrees well with most of the measurements, but some of the FTIR series in the Northern Hemisphere show a stabilisation or even a decrease in the last few years. In general, for all three gases, the measured trends vary more strongly with latitude and hemisphere than the modelled trends. Relative to the FTIR measurements, the models tend to underestimate the decreasing chlorine trends and to overestimate the fluorine increase in the Northern Hemisphere. At most sites, the models simulate a stronger decrease of ClONO2 than of HCl. In the FTIR measurements, this difference between the trends of HCl and ClONO2 depends strongly on latitude, especially in the Northern Hemisphere.

Hydrogen chloride (HCl) and hydrogen fluoride (HF) are respectively the main chlorine and fluorine reservoirs in the Earth's stratosphere. Their buildup resulted from the intensive use of man-made halogenated source gases, in particular CFC-11 (CCl3F) and CFC-12 (CCl2F2), during the second half of the 20th century. It is important to continue monitoring the evolution of these source gases and reservoirs, in support of the Montreal Protocol and also indirectly of the Kyoto Protocol. The Atmospheric Chemistry Experiment Fourier Transform Spectrometer (ACE-FTS) is a space-based instrument that has been performing regular solar occultation measurements of over 30 atmospheric gases since early 2004. In this validation paper, the HCl, HF, CFC-11 and CFC-12 version 2.2 profile data products retrieved from ACE-FTS measurements are evaluated. Volume mixing ratio profiles have been compared to observations made from space by MLS and HALOE, and from stratospheric balloons by SPIRALE, FIRS-2 and Mark-IV. Partial columns derived from the ACE-FTS data were also compared to column measurements from ground-based Fourier transform instruments operated at 12 sites. ACE-FTS data recorded from March 2004 to August 2007 have been used for the comparisons. These data are representative of a variety of atmospheric and chemical situations, with sounded air masses extending from the winter vortex to summer sub-tropical conditions. Typically, the ACE-FTS products are available in the 10–50 km altitude range for HCl and HF, and in the 7–20 and 7–25 km ranges for CFC-11 and -12, respectively. For both reservoirs, comparison results indicate an agreement generally better than 5–10% above 20 km altitude, when accounting for the known offset affecting HALOE measurements of HCl and HF. Larger positive differences are however found for comparisons with single profiles from FIRS-2 and SPIRALE. For CFCs, the few coincident measurements available suggest that the differences probably remain within ±20%.

The Atmospheric Chemistry Experiment (ACE) satellite was launched on 12 August 2003. Its two instruments measure vertical profiles of over 30 atmospheric trace gases by analyzing solar occultation spectra in the ultraviolet/visible and infrared wavelength regions. The reservoir gases HNO3, ClONO2, and N2O5 are three of the key species provided by the primary instrument, the ACE Fourier Transform Spectrometer (ACE-FTS). This paper describes the ACE-FTS version 2.2 data products, including the N2O5 update, for the three species and presents validation comparisons with available observations. We have compared volume mixing ratio (VMR) profiles of HNO3, ClONO2, and N2O5 with measurements by other satellite instruments (SMR, MLS, MIPAS), aircraft measurements (ASUR), and single balloon-flights (SPIRALE, FIRS-2). Partial columns of HNO3 and ClONO2 were also compared with measurements by ground-based Fourier Transform Infrared (FTIR) spectrometers. Overall the quality of the ACE-FTS v2.2 HNO3 VMR profiles is good from 18 to 35 km. For the statistical satellite comparisons, the mean absolute differences are generally within ±1 ppbv ±20%) from 18 to 35 km. For MIPAS and MLS comparisons only, mean relative differences lie within±10% between 10 and 36 km. ACE-FTS HNO3 partial columns (~15–30 km) show a slight negative bias of −1.3% relative to the ground-based FTIRs at latitudes ranging from 77.8° S–76.5° N. Good agreement between ACE-FTS ClONO2 and MIPAS, using the Institut für Meteorologie und Klimaforschung and Instituto de Astrofísica de Andalucía (IMK-IAA) data processor is seen. Mean absolute differences are typically within ±0.01 ppbv between 16 and 27 km and less than +0.09 ppbv between 27 and 34 km. The ClONO2 partial column comparisons show varying degrees of agreement, depending on the location and the quality of the FTIR measurements. Good agreement was found for the comparisons with the midlatitude Jungfraujoch partial columns for which the mean relative difference is 4.7%. ACE-FTS N2O5 has a low bias relative to MIPAS IMK-IAA, reaching −0.25 ppbv at the altitude of the N2O5 maximum (around 30 km). Mean absolute differences at lower altitudes (16–27 km) are typically −0.05 ppbv for MIPAS nighttime and ±0.02 ppbv for MIPAS daytime measurements.

We present a retrieval method for ammonia (NH3) total columns from ground-based Fourier transform infrared (FTIR) observations. Observations from Bremen (53.10° N, 8.85° E), Lauder (45.04° S, 169.68° E), Reúnion (20.9° S, 55.50° E) and Jungfraujoch (46.55° N, 7.98° E) were used to illustrate the capabilities of the method. NH3 mean total columns ranging 3 orders of magnitude were obtained, with higher values at Bremen (mean of 13.47 × 1015 molecules cm-2) and lower values at Jungfraujoch (mean of 0.18 × 1015 molecules cm-2). In conditions with high surface concentrations of ammonia, as in Bremen, it is possible to retrieve information on the vertical gradient, as two layers can be distinguished. The retrieval there is most sensitive to ammonia in the planetary boundary layer, where the trace gas concentration is highest. For conditions with low concentrations, only the total column can be retrieved. Combining the systematic and random errors we have a mean total error of 26 % for all spectra measured at Bremen (number of spectra (N)= 554), 30 % for all spectra from Lauder (N = 2412), 25 % for spectra from Reúnion (N = 1262) and 34 % for spectra measured at Jungfraujoch (N = 2702). The error is dominated by the systematic uncertainties in the spectroscopy parameters. Station-specific seasonal cycles were found to be consistent with known seasonal cycles of the dominant ammonia sources in the station surroundings. The developed retrieval methodology from FTIR instruments provides a new way of obtaining highly time-resolved measurements of ammonia burdens. FTIR-NH3 observations will be useful for understanding the dynamics of ammonia concentrations in the atmosphere and for satellite and model validation. It will also provide additional information to constrain the global ammonia budget., SCOPUS: ar.j, info:eu-repo/semantics/published

Harmonized time series of column-averaged mole fractions of atmospheric methane and ethane over the period 1999–2014 are derived from solar Fourier transform infrared (FTIR) measurements at the Zugspitze summit (47° N, 11° E; 2964 m a.s.l.) and at Lauder (45° S, 170° E; 370 m a.s.l.). Long-term trend analysis reveals a consistent renewed methane increase since 2007 of 6.2 [5.6, 6.9] ppb yr−1 (parts-per-billion per year) at the Zugspitze and 6.0 [5.3, 6.7] ppb yr−1 at Lauder (95 % confidence intervals). Several recent studies provide pieces of evidence that the renewed methane increase is most likely driven by two main factors: (i) increased methane emissions from tropical wetlands, followed by (ii) increased thermogenic methane emissions due to growing oil and natural gas production. Here, we quantify the magnitude of the second class of sources, using long-term measurements of atmospheric ethane as a tracer for thermogenic methane emissions. In 2007, after years of weak decline, the Zugspitze ethane time series shows the sudden onset of a significant positive trend (2.3 [1.8, 2.8] × 10−2 ppb yr−1 for 2007–2014), while a negative trend persists at Lauder after 2007 (−0.4 [−0.6, −0.1] × 10−2 ppb yr−1). Zugspitze methane and ethane time series are significantly correlated for the period 2007–2014 and can be assigned to thermogenic methane emissions with an ethane-to-methane ratio (EMR) of 12–19 %. We present optimized emission scenarios for 2007–2014 derived from an atmospheric two-box model. From our trend observations we infer a total ethane emission increase over the period 2007–2014 from oil and natural gas sources of 1–11 Tg yr−1 along with an overall methane emission increase of 24–45 Tg yr−1. Based on these results, the oil and natural gas emission contribution (C) to the renewed methane increase is deduced using three different emission scenarios with dedicated EMR ranges. Reference scenario 1 assumes an oil and gas emission combination with EMR = 7.0–16.2 %, which results in a minimum contribution C > 39 % (given as lower bound of 95 % confidence interval). Beside this most plausible scenario 1, we consider two less realistic limiting cases of pure oil-related emissions (scenario 2 with EMR = 16.2–31.4 %) and pure natural gas sources (scenario 3 with EMR = 4.4–7.0 %), which result in C > 18 % and C > 73 %, respectively. Our results suggest that long-term observations of column-averaged ethane provide a valuable constraint on the source attribution of methane emission changes and provide basic knowledge for developing effective climate change mitigation strategies.

Recently, it was shown that of the ozone-depleting substances currently emitted, N2O emissions (the primary source of stratospheric NOx) dominate, and are likely to do so throughout the 21st century. To investigate the links between N2O and NOx concentrations, and the effects of NOx on ozone in a changing climate, the evolution of stratospheric ozone from 1960 to 2100 was simulated using the NIWA-SOCOL chemistry-climate model. The yield of NOx from N2O is reduced due to stratospheric cooling and a strengthening of the Brewer-Dobson circulation. After accounting for the reduced NOx yield, additional weakening of the primary NOx cycle is attributed to reduced availability of atomic oxygen, due to a) stratospheric cooling decreasing the atomic oxygen/ozone ratio, and b) enhanced rates of chlorine-catalyzed ozone loss cycles around 2000 and enhanced rates of HOx-induced ozone depletion. Our results suggest that the effects of N2O on ozone depend on both the radiative and chemical environment of the upper stratosphere, specifically CO2-induced cooling of the stratosphere and elevated CH4 emissions which enhance HOx-induced ozone loss and remove the availability of atomic oxygen to participate in NOx ozone loss cycles.

International audience; We use observations of N2O and mean age to identify realistic transport in models in order to explain their ozone predictions. The results are applied to 15 chemistry climate models (CCMs) participating in the 2010 World Meteorological Organization ozone assessment. Comparison of the observed and simulated N2O, mean age and their compact correlation identifies models with fast or slow circulations and reveals details of model ascent and tropical isolation. This process-oriented diagnostic is more useful than mean age alone because it identifies models with compensating transport deficiencies that produce fortuitous agreement with mean age. The diagnosed model transport behavior is related to a model's ability to produce realistic lower stratosphere (LS) O3 profiles. Models with the greatest tropical transport problems compare poorly with O3 observations. Models with the most realistic LS transport agree more closely with LS observations and each other. We incorporate the results of the chemistry evaluations in the Stratospheric Processes and their Role in Climate (SPARC) CCMVal Report to explain the range of CCM predictions for the return-to-1980 dates for global (60°S-60°N) and Antarctic column ozone. Antarctic O3 return dates are generally correlated with vortex Cly levels, and vortex Cly is generally correlated with the model's circulation, although model Cl chemistry and conservation problems also have a significant effect on return date. In both regions, models with good LS transport and chemistry produce a smaller range of predictions for the return-to-1980 ozone values. This study suggests that the current range of predicted return dates is unnecessarily broad due to identifiable model deficiencies.

International audience; Coupled chemistry-climate model simulations covering the recent past and continuing throughout the 21st century have been completed with a range of different models. Common forcings are used for the halogen amounts and greenhouse gas concentrations, as expected under the Montreal Protocol (with amendments) and Intergovernmental Panel on Climate Change A1b Scenario. The simulations of the Antarctic ozone hole are compared using commonly used diagnostics: the minimum ozone, the maximum area of ozone below 220 DU, and the ozone mass deficit below 220 DU. Despite the fact that the processes responsible for ozone depletion are reasonably well understood, a wide range of results is obtained. Comparisons with observations indicate that one of the reasons for the model underprediction in ozone hole area is the tendency for models to underpredict, by up to 35%, the area of low temperatures responsible for polar stratospheric cloud formation. Models also typically have species gradients that are too weak at the edge of the polar vortex, suggesting that there is too much mixing of air across the vortex edge. Other models show a high bias in total column ozone which restricts the size of the ozone hole (defined by a 220 DU threshold). The results of those models which agree best with observations are examined in more detail. For several models the ozone hole does not disappear this century but a small ozone hole of up to three million square kilometers continues to occur in most springs even after 2070.

[1] This study examines how the stratospheric conversion of organic molecules containing chlorine (CCl y ) to inorganic forms (Cl y ) can be comprehensively evaluated in three-dimensional coupled chemistry-climate models (CCMs) using results from two models (SOCOL and UMETRAC) as examples. Stratospheric inorganic chlorine concentrations depend on both photochemistry and transport. The CCl y to Cly conversion process is the first step towards chlorine catalyzed destruction of stratospheric ozone. It is therefore important that models used for the prediction of future stratospheric change accurately simulate this process. Also, because there are multiple processes influencing Cl y in CCMs, direct comparison of Cl y by itself is of limited use as a validation diagnostic for CCMs. Results show that SOCOL's representation of the photochemical conversion of CCl y to Cl y is more realistic than UMETRAC's. The CCl y to Cl y parameterization used in UMETRAC masks transport deficiencies in the model which means that Cl y in the polar lower stratosphere from UMETRAC compares better with observations than SOCOL.

Spectral measurements of UV irradiances at Tokyo are compared with corresponding measurements at a pristine site (Lauder New Zealand) to identify the causes of the reductions in urban UV irradiances, and to quantify their effects. Tropospheric extinctions in Tokyo were found to be up to ~40% greater than at Lauder. Most of these differences can be explained by differences in cloud and aerosols, but ozone differences are also important in the summer. Examining spectral signatures of tropospheric transmission of both sites shows that reductions due to mean NO2 and SO2 amounts are generally small. However, at times the amount of NO2 can be 10 times higher than the mean amount, and on these days it can decrease the UVA irradiance up to 40%. If SO2 shows comparable day to day variability, it would contribute to significant reductions in UVB irradiances. The results indicate that at Tokyo, interactions between the larger burden of tropospheric ozone and aerosols also have a significant effect. These results have important implications for our ability to accurately retrieve surface UV irradiances at polluted sites from satellites that use backscattered UV. Supplementary data characterising these boundary layer effects are probably needed.

One of the most significant events in the evolution of the ozone layer over southern mid-latitudes since the late 1970s was the large decrease observed in 1985. This event remains unexplained and a detailed investigation of the mechanisms responsible for the event has not previously been undertaken. In this study, the 1985 Southern Hemisphere mid-latitude total column ozone anomaly is analyzed in detail based on observed daily total column ozone fields, stratospheric dynamical fields, and calculated diagnostics of stratospheric mixing. The 1985 anomaly appears to result from a combination of (i) an anomaly in the meridional circulation resulting from the westerly phase of the equatorial quasi-biennial oscillation (QBO), (ii) weaker transport of ozone from its tropical mid-stratosphere source across the sub-tropical barrier to mid-latitudes related to the particular phasing of the QBO with respect to the annual cycle, and (iii) a solar cycle induced reduction in ozone. Similar QBO and solar cycle influences prevailed in 1997 and 2006 when again total column ozone was found to be suppressed over southern mid-latitudes. The results based on observations are compared and contrasted with analyses of ozone and dynamical fields from the ECHAM4.L39(DLR)/CHEM coupled chemistry-climate model (hereafter referred to as E39C). Equatorial winds in the E39C model are nudged towards observed winds between 10° S and 10° N and the ability of this model to produce an ozone anomaly in 1985, similar to that observed, confirms the role of the QBO in effecting the anomaly.

International audience; The performance of 18 coupled Chemistry Climate Models (CCMs) in the Tropical Tropopause Layer (TTL) is evaluated using qualitative and quantitative diagnostics. Trends in tropopause quantities in the tropics and the extratropical Upper Troposphere and Lower Stratosphere (UTLS) are analyzed. A quantitative grading methodology for evaluating CCMs is extended to include variability and used to develop four different grades for tropical tropopause temperature and pressure, water vapor and ozone. Four of the 18 models and the multi‐model mean meet quantitative and qualitative standards for reproducing key processes in the TTL. Several diagnostics are performed on a subset of the models analyzing the Tropopause Inversion Layer (TIL), Lagrangian cold point and TTL transit time. Historical decreases in tropical tropopause pressure and decreases in water vapor are simulated, lending confidence to future projections. The models simulate continued decreases in tropopause pressure in the 21st century, along with ∼1K increases per century in cold point tropopause temperature and 0.5–1 ppmv per century increases in water vapor above the tropical tropopause. TTL water vapor increases below the cold point. In two models, these trends are associated with 35% increases in TTL cloud fraction. These changes indicate significant perturbations to TTL processes, specifically to deep convective heating and humidity transport. Ozone in the extratropical lowermost stratosphere has significant and hemispheric asymmetric trends. O3 is projected to increase by nearly 30% due to ozone recovery in the Southern Hemisphere (SH) and due to enhancements in the stratospheric circulation. These UTLS ozone trends may have significant effects in the TTL and the troposphere.

[1] Substantial differences in summertime surface UV irradiance between New Zealand and Europe have been reported previously. The main contributors to these differences are differences in total column ozone, differences in Sun-Earth separation between the Southern Hemisphere summer (December/January) and the Northern Hemisphere summer (June/July), and differences in tropospheric pollution. Differences due to higher Northern Hemisphere aerosol extinction have been well documented. Here we present a climatology of ozone profiles measured by balloon-borne sensors launched from Lauder, New Zealand, and from Hohenpeissenberg, Germany, to show that there are also substantial differences in the shapes of ozone profiles, especially during the summer months. A radiative transfer model is then used to investigate the extent to which these profile shape differences contribute to observed UV differences. It is found that the differences in the vertical distribution of ozone amplify existing Northern and Southern Hemisphere differences in UV. Effects can be significant in the UV-B region, but the sign of the effect depends on the solar zenith angle. Consequently, the effect on daily doses of biologically harmful UV radiation is suppressed somewhat, and the differences are responsible for differences in erythemally weighted UV of only a percent or two, which is small compared with other effects. While these effects are relatively small, differences in the vertical profile of ozone can affect the accuracy of satellite retrievals of total column ozone. This analysis shows that the lower tropospheric ozone amounts at Lauder may lead to underestimations of summertime UV from satellite by ∼4% at that site.