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Hydrogen cyanide (HCN) is an important tracer of biomass burning, but there are significant uncertainties in its atmospheric budget, especially its photochemical and ocean sinks. Here we use a tracer version of the TOMCAT global 3-D chemical transport model to investigate the physical and chemical processes driving the abundance of HCN in the troposphere and stratosphere over the period 2004–2016. The modelled HCN distribution is compared with version 4.1 of the Atmospheric Chemistry Experiment Fourier transform spectrometer (ACE-FTS) HCN satellite data, which provide profiles up to around 42 km, and with ground-based column measurements from the Network for the Detection of Atmospheric Composition Change (NDACC). The long-term ACE-FTS measurements reveal the strong enhancements in upper-tropospheric HCN due to large wildfire events in Indonesia in 2006 and 2015. Our 3-D model simulations confirm previous lower-altitude balloon comparisons that the currently recommended NASA Jet Propulsion Laboratory (JPL) reaction rate coefficient of HCN with OH greatly overestimates the HCN loss. The use of the rate coefficient proposed by Kleinböhl et al. (2006) in combination with the HCN oxidation by O(1D) gives good agreement between ACE-FTS observations and the model. Furthermore, the model photochemical loss terms show that the reduction in the HCN mixing ratio with height in the middle stratosphere is mainly driven by the O(1D) sink with only a small contribution from a reaction with OH. From comparisons of the model tracers with ground-based HCN observations we test the magnitude of the ocean sink in two different published schemes (Li et al., 2000, 2003). We find that in our 3-D model the two schemes produce HCN abundances which are very different to the NDACC observations but in different directions. A model HCN tracer using the Li et al. (2000) scheme overestimates the HCN concentration by almost a factor of 2, while a HCN tracer using the Li et al. (2003) scheme underestimates the observations by about one-third. To obtain good agreement between the model and observations, we need to scale the magnitudes of the global ocean sinks by factors of 0.25 and 2 for the schemes of Li et al. (2000) and Li et al. (2003), respectively. This work shows that the atmospheric photochemical sinks of HCN now appear well constrained but improvements are needed in parameterizing the major ocean uptake sink.

The atmospheric concentration of CFC-11 (CCl3F) has declined in response to the phase-out of its production by the Montreal Protocol. Nevertheless, this atmospheric concentration decline suffered a slow-down around 2012 due to emissions from non-reported production. Since CFC-11 is one of the most important ozone-depleting chlorofluorocarbons (CFCs), its continuous monitoring is essential. We present the CFC-11 total column time series (2000-2020) retrieved in a consistent way from ground-based high-resolution solar absorption Fourier transform infrared (FTIR) spectra. These observations were recorded at two remote stations of the Network for the Detection of Atmospheric Composition Change (NDACC): the Jungfraujoch station (Northern Hemisphere) and the Lauder station (Southern Hemisphere). These time series are new. They were produced using improved line parameters and merged considering the instrument changes and setup modifications. Afterwards, they were compared with Cape Grim station in situ surface observations conducted within the Advanced Global Atmospheric Gases Experiment (AGAGE) network and with total column datasets calculated by the TOMCAT/SLIMCAT 3-D chemical transport model. Trend analyses were performed, using an advanced statistical tool, in order to identify the timing and magnitude of the trend change in both hemispheres. The observations are consistent with the model results and confirm the slowdown in the CFC-11 atmospheric concentration decay, since ≈2011 in the Northern Hemisphere, and since ≈2014 in the Southern Hemisphere.

Réunion Island is situated in the Indian Ocean and holds one of the very few atmospheric observatories in the tropical Southern Hemisphere. Moreover, it hosts experiments providing both ground-based surface and column observations of CO2, CH4, and CO atmospheric concentrations. This work presents a comprehensive study of these observations made in the capital Saint-Denis and at the high-altitude Maïdo Observatory. We used simulations of the Weather Research and Forecasting model coupled with Chemistry (WRF-Chem), in its passive tracer option (WRF-GHG), to gain more insight to the factors that determine the observed concentrations. Additionally, this study provides an evaluation of the WRF-GHG performance in a region of the globe where it has not yet been applied. A comparison of the basic meteorological fields near the surface and along atmospheric profiles showed that WRF-GHG has decent skill in reproducing these meteorological measurements, especially temperature. Furthermore, a distinct diurnal CO2 cycle with values up to 450 ppm was found near the surface in Saint-Denis, driven by local anthropogenic emissions, boundary layer dynamics, and accumulation due to low wind speed at night. Due to an overestimation of local wind speed, WRF-GHG underestimates this nocturnal buildup. At Maïdo, a similar diurnal cycle is found but with much smaller amplitude. There, surface CO2 is essentially driven by the surrounding vegetation. The hourly column-averaged mole fractions of CO2 (XCO2) of WRF-GHG and the corresponding TCCON observations were highly correlated with a Pearson correlation coefficient of 0.90. These observations represent different air masses to those near the surface; they are influenced by processes from Madagascar, Africa, and further away. The model shows contributions from fires during the Southern Hemisphere biomass burning season but also biogenic enhancements associated with the dry season. Due to a seasonal bias in the boundary conditions, WRF-GHG fails to accurately reproduce the CH4 observations at Réunion Island. Furthermore, local anthropogenic fluxes are the largest source influencing the surface CH4 observations. However, these are likely overestimated. Furthermore, WRF-GHG is capable of simulating CO levels on Réunion Island with a high precision. As to the observed CO column (XCO), we confirmed that biomass burning plumes from Africa and elsewhere are important for explaining the observed variability. The in situ observations at the Maïdo Observatory can characterize both anthropogenic signals from the coastal regions and biomass burning enhancements from afar. Finally, we found that a high model resolution of 2 km is needed to accurately represent the surface observations. At Maïdo an even higher resolution might be needed because of the complex topography and local wind patterns. To simulate the column Fourier transform infrared (FTIR) observations on the other hand, a model resolution of 50 km might already be sufficient.

African megacities suffer from air pollution and the problem is expected to worsen in the near-future, with the ongoing explosive demographic growth in these areas. The sources of pollutants in Africa are different from those found in Europe. Agricultural burnings and charcoal-based cooking largely contribute to the NO2 and HCHO burdens. However, many large African cities, such as the City of Kinshasa, capital of the Democratic Republic of Congo, do not have local pollution monitoring capabilities. In these polluted places, space-based measurements are often the only source of data available regarding air quality. Together with the validation of TROPOMI in a poorly sampled area, this context motivated ground-based DOAS observations in Kinshasa since 2017. We first operated a single-axis instrument, which we upgraded as a MAX-DOAS instrument in December 2019. We describe the observation site in Kinshasa, the MAX-DOAS instrument, and the retrievals which use the algorithmic tools developed within the FRM4DOAS project. We compare the MAX-DOAS database (2019-2023) of ground-based observations of aerosol optical thickness (AOT), NO2 and HCHO with MODIS and TROPOMI, and with simulations using the GEOS-CHEM Chemistry and Transport Model. Such comparisons enable to assess the quality of the satellite products and model performances around Kinshasa. The ground and satellite-based observations have different sensitivities to the trace gas profiles. Combining the observations and model datasets sheds light on the true atmospheric state above Kinshasa. Another objective of this work is to constrain emission inventories in central Africa.

Since the discovery of the chlorofluorocarbons (CFCs) implication in stratospheric ozone destruction, the Montreal Protocol (1987) has aimed at controlling the production of CFCs and other ozone depleting substances (ODS) in order to protect and then recover the ozone layer. Consequently, temporary substitutes for CFCs have been developed and produced by the industry. First substitute molecules were hydrochlorofluorocarbons (HCFCs), which have smaller ozone depletion potentials (ODP) than CFCs since their atmospheric lifetimes are shorter. Nevertheless, HCFCs still contain chlorine atoms and hence, also deplete the stratospheric ozone, requiring them to be banned in turn. Thus, chlorine-free molecules, i.e. hydrofluorocarbons (HFCs) such as CH2FCF3 (HFC-134a) were introduced to replace both CFCs and HCFCs. Even if HFCs do not contribute to ozone depletion, they are very powerful greenhouse gases since they have great global warming potentials (GWPs). Consequently, the Kigali amendment (2016) to the Montreal Protocol aimed for their phase-out.The atmospheric concentrations of CFCs have decreased in response to the phase-out and ban of their production by the Montreal Protocol and its subsequent amendments, while the HCFCs burden is now leveling off. In contrast, the atmospheric concentrations of HFCs have increased notably in the last two decades.We present the first retrievals of HFC-134a from Fourier Transform Infra-Red (FTIR) solar spectra obtained from a remote site of the Network for the Detection of Atmospheric Composition Change (NDACC.org): the Jungfraujoch station (Swiss Alps). We discuss of the applicability of our retrieval strategy to other NDACC sites, for future quasi global monitoring from ground-based observations. We further perform first comparisons with other datasets as ACE-FTS satellite observations.

We present a database of MAX-DOAS (Multi-AXis Differential Optical Absorption Spectroscopy) ground-based observations of NO2 and H2CO performed for the first time in the city of Kinshasa. These measurements were conducted between November 2019 and July 2021 and processed using the standardized inversion tools developed in the ESA FRM4DOAS (Fiducial Reference Measurements for Ground-Based DOAS Air-Quality Observations) project. The retrieved geophysical quantities are used to validate column observations from the TROPOspheric Monitoring Instrument (TROPOMI) in Kinshasa. In the validation, we experiment three different comparison cases of increasing complexity. In the first case, a direct comparison between MAX-DOAS observations (average +/- 60 minutes around overpass) and TROPOMI shows an underestimation of TROPOMI with a median bias of -40 % (s=0.26 and R=0.41) for NO2 and -26 % (s=0.24 and R=0.28) for H2CO. The second case takes into account the different vertical sensitivities of the two instruments and the apriori profile. We note a slight decrease of the biases and a strong improvement of the linear regression parameter, about -35 % (s=0.72 and R=0.74) for NO2 and 1 % (s=1.01 and R=0.66) for H2CO. The third case, which is considered more realistic than the first two, builds on the second case by considering also the direction of sight of the MAX-DOAS. For this third case, we find a bias of -2 % (s= 1.09; R= 0.59) for NO2 and 13 % (s= 1.51; R= 0.60) for H2CO. Those results indicate a large impact of the vertical sensitivity and horizontal heterogeneity in this validation process at this site. In order to evaluate the capability of the GEOS-Chem model in this region, we performed the comparisons between TROPOMI and the simulations made for 2020. We found a bias of 16 % (s= 0.42 and R = 0.80) for NO2 and bais of 61 % (s= 0.05 and R = 0.24) for H2CO.

Anomalies of tropospheric columns of ozone (O$_3$), carbon monoxide (CO), acetylene (C$_2$H$_2$), formaldehyde (H$_2$CO), and ethane (C$_2$H$_6$) are quantified during the 2020 stringent COVID-19 world-wide lockdown using multiple ground-based Fourier-transform infrared spectrometers covering urban and remote conditions. We applied an exponential smoothing forecasting approach to the data sets to estimate business-as-usual values for 2020, which are then contrasted with actual observations. The Community Atmosphere Model with chemistry (CAM-chem) is used to simulate the same gases using lockdown-adjusted and business-as-usual emissions. The role of meteorology, or natural variability, is assessed with additional CAM-chem simulations. The tropospheric column of O$_3$ declined between March and May 2020 for most sites with a mean decrease of 9.2% ± 4.7%. Simulations reproduce these anomalies, especially under background conditions where natural variability explains up to 80% of the decline for sites in the Northern Hemisphere. While urban sites show a reduction between 1% and 12% in tropospheric CO, the remote sites do not show a significant change. Overall, CAM-chem simulations capture the magnitude of the anomalies and in many cases natural variability and lockdowns have opposite effects. We further used the long-term record of the Measurements of Pollution in the Troposphere (MOPITT) satellite instrument to capture global anomalies of CO. Reductions of CO vary highly across regions but North America and Europe registered lower values in March 2020. The absence of CO reduction in April and May, concomitant with reductions of anthropogenic emissions, is explained by a negative anomaly in the hydroxyl radical (OH) found with CAM-chem. The implications of these findings are discussed for methane (CH$_4$), which shows a positive lifetime anomaly during the COVID-19 lockdown period. The fossil fuel combustion by-product tracer C2H2 shows a mean drop of 13.6% ± 8.3% in urban Northern Hemisphere sites due to the reduction in emissions and in some sites exacerbated by natural variability. For some sites with anthropogenic influence there is a decrease in C$_2$H$_6$. The simulations capture the anomalies but the main cause may be related to natural variability. H$_2$CO declined during the stringent 2020 lockdown in all urban sites explained by reductions in emissions of precursors.

Synthetic halogenated organic chlorofluorocarbons (CFCs) play an important role in stratospheric ozone depletion and contribute significantly to the greenhouse effect. In this work, the mid-infrared solar spectra measured by ground-based high-resolution Fourier transform infrared spectroscopy (FTIR) were used to retrieve atmospheric CFC-11 (CCl3F) and CFC-12 (CCl2F2) at Hefei, China. The CFC-11 columns observed from January 2017 to December 2020 and CFC-12 columns from September 2015 to December 2020 show a similar annual decreasing trend and seasonal cycle, with an annual rate of -0.47±0.06 % yr−1 and -0.68±0.03 % yr−1, respectively. So the decline rate of CFC-11 is significantly lower than that of CFC-12. CFC-11 total columns were higher in summer, and CFC-12 total columns were higher in summer and autumn. Both CFC-11 and CFC-12 total columns reached the lowest in spring. Further, FTIR data of NDACC (Network for the Detection of Atmospheric Composition Change) candidate station Hefei were compared with the ACE-FTS (Atmospheric Chemistry Experiment Fourier transform spectrometer) satellite data, WACCM (Whole Atmosphere Community Climate Model) data, and the data from other NDACC-IRWG (InfraRed Working Group) stations (St. Petersburg, Jungfraujoch, and Réunion). The mean relative difference between the vertical profiles observed by FTIR and ACE-FTS is -5.6±3.3 % and 4.8±0.9 % for CFC-11 and CFC-12 for an altitude of 5.5 to 17.5 km, respectively. The results demonstrate that our FTIR data agree relatively well with the ACE-FTS satellite data. The annual decreasing rate of CFC-11 measured from ACE-FTS and calculated by WACCM is -1.15±0.22 % yr−1 and -1.68±0.18 % yr−1, respectively. The interannual decreasing rates of atmospheric CFC-11 obtained from ACE-FTS and WACCM data are higher than that from FTIR observations. Also, the annual decreasing rate of CFC-12 from ACE-FTS and WACCM is -0.85±0.15 % yr−1 and -0.81±0.05 % yr−1, respectively, close to the corresponding values from the FTIR measurements. The total columns of CFC-11 and CFC-12 at the Hefei and St. Petersburg stations are significantly higher than those at the Jungfraujoch and Réunion (Maïdo) stations, and the two values reached the maximum in local summer or autumn and the minimum in local spring or winter at the four stations. The seasonal variability at the three stations in the Northern Hemisphere is higher than that at the station in the Southern Hemisphere.

This study presents an updated evaluation of stratospheric ozone profile trends in the 60∘ S–60∘ N latitude range over the 2000–2020 period using an updated version of the Long-term Ozone Trends and Uncertainties in the Stratosphere (LOTUS) regression model that was used to evaluate such trends up to 2016 for the last WMO Ozone Assessment (2018). In addition to the derivation of detailed trends as a function of latitude and vertical coordinates, the regressions are performed with the datasets averaged over broad latitude bands, i.e. 60–35∘ S, 20∘ S–20∘ N and 35–60∘ N. The same methodology as in the last assessment is applied to combine trends in these broad latitude bands in order to compare the results with the previous studies. Longitudinally resolved merged satellite records are also considered in order to provide a better comparison with trends retrieved from ground-based records, e.g. lidar, ozonesondes, Umkehr, microwave and Fourier transform infrared (FTIR) spectrometers at selected stations where long-term time series are available. The study includes a comparison with trends derived from the REF-C2 simulations of the Chemistry Climate Model Initiative (CCMI-1). This work confirms past results showing an ozone increase in the upper stratosphere, which is now significant in the three broad latitude bands. The increase is largest in the Northern and Southern Hemisphere midlatitudes, with ∼2.2 ± 0.7 % per decade at ∼2.1 hPa and ∼2.1 ± 0.6 % per decade at ∼3.2 hPa respectively compared to ∼1.6 ± 0.6 % per decade at ∼2.6 hPa in the tropics. New trend signals have emerged from the records, such as a significant decrease in ozone in the tropics around 35 hPa and a non-significant increase in ozone in the southern midlatitudes at about 20 hPa. Non-significant negative ozone trends are derived in the lowermost stratosphere, with the most pronounced trends in the tropics. While a very good agreement is obtained between trends from merged satellite records and the CCMI-1 REF-C2 simulation in the upper stratosphere, observed negative trends in the lower stratosphere are not reproduced by models at southern and, in particular, at northern midlatitudes, where models report an ozone increase. However, the lower-stratospheric trend uncertainties are quite large, for both measured and modelled trends. Finally, 2000–2020 stratospheric ozone trends derived from the ground-based and longitudinally resolved satellite records are in reasonable agreement over the European Alpine and tropical regions, while at the Lauder station in the Southern Hemisphere midlatitudes they show some differences.

Ethane ( C2H6 ) is an important greenhouse gas and plays a significant role in tropospheric chemistry and climate change. This study first presents and then quantifies the variability, sources, and transport of C2H6 over densely populated and highly industrialized eastern China using ground-based high-resolution Fourier transform infrared (FTIR) remote sensing along with atmospheric modeling techniques. We obtained a retrieval error of 6.21 ± 1.2 (1 σ )% and degrees of freedom (DOFS) of 1.47 ± 0.2 (1 σ ) in the retrieval of C2H6 tropospheric column-averaged dry-air mole fraction (troDMF) over Hefei, eastern China (32 ∘ N, 117 ∘ E; 30 m a . s . l . ). The observed C2H6 troDMF reached a minimum monthly mean value of 0.36 ± 0.26 ppbv in July and a maximum monthly mean value of 1.76 ± 0.35 ppbv in December, and showed a negative change rate of − 2.60 ± 1.34 % yr−1 from 2015 to 2020. The dependencies of C2H6 troDMF on meteorological and emission factors were analyzed using generalized additive models (GAMs). Generally, both meteorological and emission factors have positive influences on C2H6 troDMF in the cold season (December–January–February/March–April–May, DJF/MAM) and negative influences on C2H6 troDMF in the warm season (June–July–August/September–October–November, JJA/SON). GEOS-Chem chemical model simulation captured the observed C2H6 troDMF variability and was, thus, used for source attribution. GEOS-Chem model sensitivity simulations concluded that the anthropogenic emissions (fossil fuel plus biofuel emissions) and the natural emissions (biomass burning plus biogenic emissions) accounted for 48.1 % and 39.7 % of C2H6 troDMF variability over Hefei, respectively. The observed C2H6 troDMF variability mainly results from the emissions within China (74.1 %), where central, eastern, and northern China dominated the contribution (57.6 %). Seasonal variability in C2H6 transport inflow and outflow over the observation site is largely related to the midlatitude westerlies and the Asian monsoon system. Reduction in C2H6 abundance from 2015 to 2020 mainly results from the decrease in local and transported C2H6 emissions, which points to air quality improvement in China in recent years.

The Brewer-Dobson Circulation (BDC) determines the distribution of long-lived tracers in the stratosphere; therefore, their changes can be used to diagnose changes in the BDC. We investigate decadal (2005-2018) trends of nitrous oxide (N2O) stratospheric columns (12-40 km) as measured by four Fourier transform infrared (FTIR) ground-based instruments and by the Atmospheric Chemistry Experiment Fourier Transform Spectrometer (ACE-FTS), and compare them with simulations by two models: a chemistry-transport model (CTM) driven by four different reanalyses, and the Whole Atmosphere Chemistry-Climate Model (WACCM). The limited sensitivity of the FTIR instruments can hide negative N2O trends in the mid-stratosphere because of the large increase in the lowermost stratosphere. When applying the ACE-FTS sampling on model datasets, the reanalyses by the European Centre for Medium Range Weather Forecast (ECMWF) compare best with ACE-FTS, but the N2O trends are consistently exaggerated. Model sensitivity tests show that while decadal N2O trends reflect changes in transport, these trends are less significant in the northern extratropics due to the larger variability of transport over timescales shorter than two years in that region. We further investigate the N2O Transformed Eulerian Mean (TEM) budget in three model datasets. The TEM analysis shows that enhanced advection affects the stratospheric N2O trends more than changes in mixing. While no ideal observational dataset currently exists, this model study of N2O trends still provides new insights about the BDC and its changes thanks to relevant sensitivity tests and the TEM analysis.

Réunion is a French island in the Indian Ocean, which holds one of the very few atmospheric observatories in the tropical Southern Hemisphere. Moreover, it hosts experiments providing both ground-based in situ and column Fourier Transform InfraRed spectrometer (FTIR) observations of CO2, CH4 and CO atmospheric concentrations, contributing to the Integrated Carbon Observation System (ICOS), the Network for the Detection of Atmospheric Composition Change (NDACC) and the Total Carbon Column Observing Network (TCCON). This work presents a comprehensive study of these observations made in the capital Saint-Denis and at the high-altitude Maïdo Observatory. We used simulations of the Weather Research and Forecasting model coupled with chemistry (WRF-Chem), in its passive tracer option (WRF-GHG), to gain more insight in the factors that determine these concentrations. Additionally, this study provides an evaluation of the WRF-GHG performance in a region where it has not yet been applied.This presentation discusses the model set-up and the main findings from the comparisons between the observations and the model simulations, as summarized hereafter.A comparison of the meteorology near the surface and along atmospheric profiles showed that WRF-GHG has decent skill in reproducing these measurements, especially temperature. Surface CO2 in Saint-Denis follows a distinct diurnal cycle with values up to 450 ppm at night, driven by local anthropogenic emissions, boundary layer dynamics and accumulation due to low wind speeds. Due to an overestimation of local wind speeds, WRF-GHG underestimates this nocturnal buildup. At Maïdo, a similar diurnal cycle is found but with much smaller amplitude. There, surface CO2 is essentially driven by the surrounding vegetation. A high correlation was found between the hourly XCO2 of WRF-GHG and the corresponding TCCON observations. These represent different air masses than those near the surface. They are influenced by processes from distant areas such as Africa and Madagascar. The model shows contributions from fires during the biomass burning (BB) season, but also positive biogenic enhancements associated with the dry season. WRF-GHG fails to reproduce the CH4 observations at Réunion accurately due to a seasonal bias in the background arising from the CAMS reanalysis boundary conditions. Further, local anthropogenic fluxes are the largest source influencing the surface observations at Réunion. However in Saint-Denis, and even more so at Maïdo, the anthropogenic CH4 emissions from EDGAR are likely overestimated. WRF-GHG is able to simulate the CO levels at Réunion with a relative high degree of accuracy. As to the observed XCO, the importance of BB plumes from Africa and elsewhere for explaining the observed variability is confirmed. The surface observations at Maïdo can detect anthropogenic signals from the coastlands during the day and BB enhancements from afar at night, when the Observatory is located in the boundary layer and the free troposphere, respectively.The high model resolution of 2km is needed to accurately represent the surface observations. Because of the complex topography and local dynamics, an even higher resolution might be needed at Maïdo. To simulate the column observations on the other hand, a model resolution of 50km might already be sufficient.

We present a multiyear time series of column abundances of carbon monoxide (CO), hydrogen cyanide (HCN), and ethane (C2H6) measured using Fourier-transform infrared (FTIR) spectrometers at 10 sites affiliated with the Network for the Detection of Atmospheric Composition Change (NDACC). Six are high-latitude sites: Eureka, Ny-Ålesund, Thule, Kiruna, Poker Flat, and St. Petersburg, and four are midlatitude sites: Zugspitze, Jungfraujoch, Toronto, and Rikubetsu. For each site, the interannual trends and seasonal variabilities of the CO time series are accounted for, allowing background column amounts to be determined. Enhancements above the seasonal background were used to identify possible wildfire pollution events. Since the abundance of each trace gas emitted in a wildfire event is specific to the type of vegetation burned and the burning phase, correlations of CO to the long-lived wildfire tracers HCN and C2H6 allow for further confirmation of the detection of wildfire pollution. A GEOS-Chem tagged CO simulation with Global Fire Assimilation System (GFASv1.2) biomass burning emissions was used to determine the source attribution of CO concentrations at each site from 2003 to 2018. For each detected wildfire pollution event, FLEXPART back-trajectory simulations were performed to determine the transport times of the smoke plume. Accounting for the loss of each species during transport, the enhancement ratios of HCN and C2H6 with respect to CO were converted to emission ratios. We report mean emission ratios with respect to CO for HCN and C2H6 of 0.0047 and 0.0092, respectively, with a standard deviation of 0.0014 and 0.0046, respectively, determined from 23 boreal North American wildfire events. Similarly, we report mean emission ratios for HCN and C2H6 of 0.0049 and 0.0100, respectively, with a standard deviation of 0.0025 and 0.0042, respectively, determined from 39 boreal Asian wildfire events. The agreement of our emission ratios with literature values illustrates the capability of ground-based FTIR measurements to quantify biomass burning emissions. We provide a comprehensive dataset that quantifies HCN and C2H6 emission ratios from 62 wildfire pollution events. Our dataset provides novel emission ratio estimates, which are sparsely available in the published literature, particularly for boreal Asian sources.

Carbonyl sulfide (OCS) is a non-hygroscopic trace species in the free troposphere and a large sulfur reservoir maintained by both direct oceanic, geologic, biogenic, and anthropogenic emissions and the oxidation of other sulfur-containing source species. It is the largest source of sulfur transported to the stratosphere during volcanically quiescent periods. Data from 22 ground-based globally dispersed stations are used to derive trends in total and partial column OCS. Middle infrared spectral data are recorded by solar-viewing Fourier transform interferometers that are operated as part of the Network for the Detection of Atmospheric Composition Change between 1986 and 2020. Vertical information in the retrieved profiles provides analysis of discreet altitudinal regions. Trends are found to have well-defined inflection points. NASA | Science Mission Directorate (SMD). Grant Numbers: NNX17AE38 G S003, 80NSSC21K0891. Natural Sciences and Engineering Research Council of Canada (NSERC); the Canadian Space Agency (CSA); Environment and Climate Change Canada (ECCC); Sorbonne Université; French Research Center CNRS; French Space Agency CNES. F.R.S.-FNRS. Grant Numbers: J.0147.18, J.0126.21. CONACYT. Grant Number: 290589. PAPIIT. Grant Number: IN111521. NIWA; New Zealand’s Ministry of Business, Innovation and Employment Strategic Science Investment Fund German research foundation. Grant Number: 268020496 German Bundesministerium für Wirtschaft und Energie (BMWi). Grant Numbers: 50EE1711A, 50EE1711D. Helmholtz Society Australian Research Council. Université de La Réunion. Grant Numbers: LACy-UMR8105, UMS3365.

The Brewer-Dobson Circulation (BDC) determines the distribution of long-lived tracers in the stratosphere; therefore, their changes can be used to diagnose changes in the BDC. We evaluate decadal (2005-2018) trends of nitrous oxide (N

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.

We present the first ground-based remote sensing measurements of NO2 made in Kinshasa. They were performed from 2017 to 2019. The motivation of making observations on air pollution in Kinshasa comes from its geographical location, its demography, its climatic conditions and the many different sources of NO2 existing in its surroundings. A method for recovering the vertical density of the NO2 tropospheric column (VCDtropo) based on the Differential Optical Absorption Spectroscopy (DOAS) applied to observations at the zenith and 35° elevation angle is described. The mean value of VCDtropo observed in Kinshasa is 3 × 1015 molecules cm−2. We further present first comparisons with the OMI and TROPOMI satellite observations. When comparing OMI data with our observations and using a linear regression analysis, we find a slope of 0.34 and a correlation coefficient of 0.50 for 51 days of coincidences over 2017−2019. Similar comparisons with TROPOMI for 44 days show a slope of 0.41 and a correlation coefficient of 0.72. This study opens up perspectives for further air quality related studies in Kinshasa and central Africa.

Nitric oxide (NO) is a key active trace gas in the atmosphere, which contributes to form “bad” ozone (O3) in the troposphere and to the destruction of “good” O3 in the stratosphere. In this study, we present the NO retrieval from ground-based Fourier-transform infrared (FTIR) solar absorption spectrometry measurements at a polluted site (Xianghe, China) and a background site (Maïdo, Reunion Island). The Degree Of Freedom (DOF) of the NO retrieval is 2.3 ± 0.4 (1σ) at Xianghe and 1.3 ± 0.1 at Maïdo. The high NO mole fraction near the surface at Xianghe allows us to derive tropospheric and stratospheric NO partial columns separately, albeit the tropospheric column is almost not able to be retrieved in summer (June–August) because of the high water vapor abundance. At Maïdo, the NO retrieval is only sensitive to the stratosphere. The FTIR measurements at Maïdo show that the stratospheric NO partial column increases from the early morning to about 14:00 local time and starts decreasing thereafter. The stratospheric NO partial column is large in summer as compared to winter at both sites, and the seasonal variation of the FTIR stratospheric NO partial columns is consistent with that observed by the co-located Michelson Interferometer for Passive Atmospheric Sounding (MIPAS) satellite measurements. We observe a good correlation between the carbon monoxide (CO) and NO daily partial columns in the troposphere observed by the FTIR measurements at Xianghe with a correlation coefficient of 0.70, because both species have similar anthropogenic sources.

Ethane (C2H6) is an important greenhouse (GHG) gas and plays a significant role in tropospheric chemistry and climate change. This study first presents and quantifies the variability, source, and transport of C2H6 over densely populated and industrialized eastern China by using ground-based high-resolution Fourier transform infrared (FTIR) remote sensing technique. We obtained a retrieval error of 6.21 ± 1.2 (1σ) % and degrees of freedom (DOFS) of 1.47 ± 0.2 (1σ) in retrieval of C2H6 tropospheric column-averaged dry-air mole fraction (troDMF) over Hefei, eastern China (117°E, 32°N, 30 m a.s.l.). The observed C2H6 troDMF reached a minimum monthly mean value of (0.36 ± 0.26) ppbv in July and a maximum monthly mean value of (1.76 ± 0.35) ppbv in December, and showed a negative change rate of (−2.60 ± 1.34) %/yr from 2015 to 2020. The dependencies of C2H6 troDMF on meteorological and emission factors were analyzed by using generalized additive models (GAMs). Generally, both meteorological and emission factors have positive influences on C2H6 troDMF in cold season (DJF/MAM) and negative influences on C2H6 troDMF in warm season (JJA/SON). GEOS-Chem chemical model simulation captured the observed C2H6 troDMF variability and was thus used for source attribution. GEOS-Chem model sensitivity simulations concluded that the anthropogenic emissions (fossil fuel plus biofuel emissions) and the natural emissions (biomass burning plus biogenic emissions) accounted for 49.2 % and 37.1 % of C2H6 troDMF abundance over Hefei, respectively. The observed C2H6 troDMF abundance mainly results from the emissions within China (74.1 %), where central, eastern, and northern China dominated the contribution (57.6 %). Seasonal variability in C2H6 transport inflow and outflow over the observation site is largely related to the mid-latitude westerlies and Asian monsoon system. Reduction in C2H6 abundance from 2015 to 2020 mainly results from the decrease in local and transported C2H6 emissions, which points to air quality improvement in China in recent years.

The Brewer-Dobson Circulation (BDC) is a wintertime stratospheric circulation characterized by upwelling of tropospheric air in the tropics, poleward flow in the stratosphere, and downwelling at mid and high latitudes, with important implications for chemical tracer distributions, stratospheric heat and momentum budgets, and mass exchange with the troposphere. Nitrous oxide (N2O) is continuously emitted in the troposphere, where has no sinks, and transported into the stratosphere, where is destroyed by photodissociaiton. The lifetime of N2O is approximately 100 years, which makes it an excellent long-lived tracer for transport studies in the stratosphere. In this study, we investigate the long-term N2O changes in the stratosphere using a number a different datasets. We analyze the simulation from the state-of-the-art Chemistry-Climate Model WACCM (period: 1990-2014), together with the BASCOE Chemistry-Transport Model driven by five dynamical reanalyses (ERA5, ERA-Interim, JRA-55, MERRA, MERRA-2, period: 1996-2014), and the chemical reanalysis of Aura Microwave Limb Sounder version 3 (BRAM3, period: 2004-2013). We will also compare those gridded data to ground-based observations from Fourier transform infrared spectrometer at the Jungfraujoch station in the Swiss Alps. The long-term trends of the N2O concentration are investigated using the Dynamic Linear Model (DLM). The DLM is a regression model based on the Bayesian inference, which allow fitting atmospheric data with four main components: a linear trend, a seasonal cycle, a number of proxies (solar cycle, ENSO, QBO ?) and an autoregressive process. DLM has the advantage that the trend and the seasonal and regression coefficients depend on time; DLM can therefore detect changes in the recovered trend, and modulations of the amplitude of the regressors with time. Early results show that the datasets exhibit hemispheric differences in the long-term N2O changes in the lower stratosphere. In the Southern Hemisphere, the DLM fit of the N2O concentrations increases across the datasets, but the resulting trend is statistically significant only in limited regions of the stratosphere. In the Northern Hemisphere, the N2O fit does not change significantly in the considered period, resulting in a near-zero trend. These hemispheric differences are in line with previous studies of transport that identify different long-term trends of tracers and mean age of air between the hemispheres. The fit through the DLM allows the amplitude of the seasonal cycle component to vary in time. Preliminary results indicate that the time variations depend on the hemisphere in the extra-tropical regions. In the Southern Hemisphere, the datasets generally show a constant amplitude of the seasonal cycle throughout the considered periods, with the largest values in the high latitudes in response to the polar vortex. In the Northern Hemisphere, the inter-annual variations of the seasonal cycle amplitude are stronger, with BRAM3 showing the largest modulations. In addition, larger differences arise in the amplitude of the seasonal component. WACCM simulates large amplitudes of the seasonal cycle, while the reanalyses show smaller values. A more detailed analysis of the results will include ground-based observations, and the extension of the CTM runs to a longer period that matches the length of the WACCM run.

Recent studies in Kinshasa show how much air pollution is present in this large megalopolis of 13 million inhabitants, with levels even exceeding the recommended values (WHO, 2018).From May 2017 to November 2019, the University of Kinshasa (UniKin: -4.42°S, 15.31°E) has equipped itself with a low-cost instrument operating in single-axis mode. Studies based on measurements made with this instrument have demonstrated the presence of NO2 with highest vertical column densities (VCDs) in June, July and August (R. Yombo, 2020). With this low-cost instrument, information such as aerosol and NO2 profile, which have major impacts on the determination of VCDs could not be obtained, leading to considerable uncertainties in the results obtained.This work therefore supports the first one as described above, by presenting first results of a new MAX-DOAS (multi-axis differential optical absorption spectroscopy) system built at the IASB, in Belgium, and installed in Kinshsasa at the same location in November 2019. We first present the new MAX-DOAS, which is based on compact Avantes spectrometer (280-550 nm, 0.7 nm FWHM), a small computer, and a scanner. We describe the analyses for aerosol extinction, HCHO and NO2 using FRM4-DOAS. For these two molecules, we compare with model simulations (GEOS-Chem) and satellite observations (OMI, TROPOMI).

Throughout spring and summer 2020, ozone stations in the northern extratropics recorded unusually low ozone in the free troposphere. From April to August, and from 1 to 8 kilometers altitude, ozone was on average 7% (≈4 nmol/mol) below the 2000–2020 climatological mean. Such low ozone, over several months, and at so many stations, has not been observed in any previous year since at least 2000. Atmospheric composition analyses from the Copernicus Atmosphere Monitoring Service and simulations from the NASA GMI model indicate that the large 2020 springtime ozone depletion in the Arctic stratosphere contributed less than one‐quarter of the observed tropospheric anomaly. The observed anomaly is consistent with recent chemistry‐climate model simulations, which assume emissions reductions similar to those caused by the COVID‐19 crisis. COVID‐19 related emissions reductions appear to be the major cause for the observed reduced free tropospheric ozone in 2020., Plain Language Summary: Worldwide actions to contain the COVID‐19 virus have closed factories, grounded airplanes, and have generally reduced travel and transportation. Less fuel was burnt, and less exhaust was emitted into the atmosphere. Due to these measures, the concentration of nitrogen oxides and volatile organic compounds (VOCs) decreased in the atmosphere. These substances are important for photochemical production and destruction of ozone in the atmosphere. In clean or mildly polluted air, reducing nitrogen oxides and/or VOCs will reduce the photochemical production of ozone and result in less ozone. In heavily polluted air, in contrast, reducing nitrogen oxides can increase ozone concentrations, because less nitrogen oxide is available to destroy ozone. In this study, we use data from three types of ozone instruments, but mostly from ozonesondes on weather balloons. The sondes fly from the ground up to 30 kilometers altitude. In the first 8 km, we find significantly reduced ozone concentrations in the northern extratropics during spring and summer of 2020, less than in any other year since at least 2000. We suggest that reduced emissions due to the COVID‐19 crisis have lowered photochemical ozone production and have caused the observed ozone reductions in the troposphere., Key Points: In spring and summer 2020, stations in the northern extratropics report on average 7% (4 nmol/mol) less tropospheric ozone than normal Such low tropospheric ozone, over several months, and at so many sites, has not been observed in any previous year since at least 2000 Most of the reduction in tropospheric ozone in 2020 is likely due to emissions reductions related to the COVID‐19 pandemic, NASA | Earth Sciences Division (NASA Earth Science Division) http://dx.doi.org/10.13039/100014573, Gouvernement du Canada | Natural Sciences and Engineering Research Council of Canada (NSERC) http://dx.doi.org/10.13039/501100000038, Australian Research Council, Fonds De La Recherche Scientifique ‐ FNRS (FNRS) http://dx.doi.org/10.13039/501100002661, Deutsche Forschungsgemeinschaft (DFG) http://dx.doi.org/10.13039/501100001659, Bundesministerium für Wirtschaft und Energie (BMWi) http://dx.doi.org/10.13039/501100006360

The Sentinel-5 Precursor (S5P) mission with the TROPOspheric Monitoring Instrument (TROPOMI) onboard has been measuring solar radiation backscattered by the Earth's atmosphere and its surface since its launch on 13 October 2017. Methane (CH4) and carbon monoxide (CO) data with a spatial resolution (initially 7 x 7 km2, upgraded to 5.5 x 7 km2 on 6th of August 2019) have been retrieved from shortwave infrared (SWIR) and near-infrared (NIR) measurements since the end of November 2017 and made available to the experts for early validation and quality checks before the official product release. In this paper, we present for the first time the S5P CH4 and CO validation results (covering a period from November 2017 to September 2020) using global Total Carbon Column Observing Network (TCCON) and Infrared Working Group of the Network for the Detection of Atmospheric Composition Change (NDACC-IRWG) network data, accounting for a priori alignment and smoothing uncertainties in the validation, and testing the sensitivity of validation results towards the application of advanced co-location criteria.We found that the required bias (systematic error) of 1.5 % and random error of 1 % for the S5P standard and bias-corrected methane data are met for measurements over land surfaces with pixels having quality assurance (QA) value > 0.5. The systematic difference between the S5P standard XCH4 and TCCON data is on average −0.69 ± 0.73 %. The systematic difference changes to a value of −0.25 ± 0.57 % for the S5P bias-corrected XCH4 data. We found a correlation of above 0.6 for most stations, which is mostly dominated by the seasonal cycle. The contributions of smoothing uncertainty at the individual stations are estimated and found to be dependent on the location. The highest contribution of the smoothing uncertainty is observed for mid-latitude TCCON stations and high latitude stations for NDACC. A seasonal dependency of the relative bias is seen. We observe a high bias during the springtime measurements at high SZA and a decreasing bias with increasing SZA for the rest of the year.We found that the required bias (systematic error) of 15 % and random error of < 10 % for the S5P carbon monoxide data are met in general for measurements over all surfaces with pixels having quality assurance value of > 0.5. There are a few stations where this is not the case, mostly due to co-location mismatches and the limited availability of co-located data. We compared the S5P XCO data with respect to standard TCCON XCO and unscaled TCCON XCO (without application of the empirical scaling factor) data sets. The systematic difference between the S5P XCO and the TCCON data is on average 9.14 ± 3.33 % (standard TCCON XCO data) and 2.36 ± 3.22 % (unscaled TCCON XCO data). We found that the systematic difference between the S5P CO column and NDACC CO column data (excluding two stations that were obvious outliers) is on average 6.44 ± 3.79 %. We found a correlation of above 0.9 for most TCCON and NDACC stations indicating that the temporal variations in CO column captured by the ground-based instruments are reproduced very similarly by the S5P CO column. The contribution of smoothing uncertainty at the individual stations is estimated and found to be significant. They are found to be dependent on the location with large changes seen for stations located in the Southern Hemisphere as compared to the Northern Hemisphere and at highly polluted stations. A cone co-location criterion, which gives a better match between the ground-based instrument's line-of-sight and satellite pixels, seems to give better results for high latitude stations and stations located close to emission sources. The validation results for the clear-sky and cloud cases of S5P pixels are comparable to the validation results including all pixels with quality assurance value of > 0.5. We observe that the relative bias increases with increasing SZA. We estimated this increase is about 10 % over the complete range of measurement SZAs.The study shows the high quality of S5P CH4 and CO data by validating the products against reference global TCCON and NDACC stations covering a wide range of latitudinal bands, atmospheric conditions, and surface conditions.

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

Emissions of C 2 -C 5 alkanes from the U.S. oil and gas sector have changed rapidly over the last decade. We use a nested GEOS-Chem simulation driven by updated 2011NEI emissions with aircraft, surface, and column observations to (1) examine spatial patterns in the emissions and observed atmospheric abundances of C 2 -C 5 alkanes over the United States and (2) estimate the contribution of emissions from the U.S. oil and gas industry to these patterns. The oil and gas sector in the updated 2011NEI contributes over 80% of the total U.S. emissions of ethane (C 2 H 6 ) and propane (C 3 H 8 ), and emissions of these species are largest in the central United States. Observed mixing ratios of C 2 -C 5 alkanes show enhancements over the central United States below 2 km. A nested GEOS-Chem simulation underpredicts observed C 3 H 8 mixing ratios in the boundary layer over several U.S. regions, and the relative underprediction is not consistent, suggesting C 3 H 8 emissions should receive more attention moving forward. Our decision to consider only C 4 -C 5 alkane emissions as a single lumped species produces a geographic distribution similar to observations. Due to the increasing importance of oil and gas emissions in the United States, we recommend continued support of existing long-term measurements of C 2 -C 5 alkanes. We suggest additional monitoring of C 2 -C 5 alkanes downwind of northeastern Colorado, Wyoming, and western North Dakota to capture changes in these regions. The atmospheric chemistry modeling community should also evaluate whether chemical mechanisms that lump larger alkanes are sufficient to understand air quality issues in regions with large emissions of these species., SCOPUS: ar.j, info:eu-repo/semantics/published

The Brewer–Dobson circulation (BDC) is a stratospheric circulation characterized by upwelling of tropospheric air in the tropics, poleward flow in the stratosphere, and downwelling at mid and high latitudes, with important implications for chemical tracer distributions, stratospheric heat and momentum budgets, and mass exchange with the troposphere. As the photochemical losses of nitrous oxide ( N2O ) are well known, model differences in its rate of change are due to transport processes that can be separated into the mean residual advection and the isentropic mixing terms in the transformed Eulerian mean (TEM) framework. Here, the climatological impact of the stratospheric BDC on the long-lived tracer N2O is evaluated through a comparison of its TEM budget in the Whole Atmosphere Community Climate Model (WACCM), in a chemical reanalysis of the Aura Microwave Limb Sounder version 2 (BRAM2) and in a chemistry transport model (CTM) driven by four modern reanalyses: the European Centre for Medium-Range Weather Forecasts Interim reanalysis (ERA-Interim; Dee et al. , 2011 ) , the Japanese 55-year Reanalysis (JRA-55; Kobayashi et al. , 2015 ) , and the Modern-Era Retrospective analysis for Research and Applications version 1 (MERRA; Rienecker et al. , 2011 ) and version 2 (MERRA-2; Gelaro et al. , 2017 ) . The effects of stratospheric transport on the N2O rate of change, as depicted in this study, have not been compared before across this variety of datasets and have never been investigated in a modern chemical reanalysis. We focus on the seasonal means and climatological annual cycles of the two main contributions to the N2O TEM budget: the vertical residual advection and the horizontal mixing terms. The N2O mixing ratio in the CTM experiments has a spread of approximately ∼20 % in the middle stratosphere, reflecting the large diversity in the mean age of air obtained with the same CTM experiments in a previous study. In all datasets, the TEM budget is closed well; the agreement between the vertical advection terms is qualitatively very good in the Northern Hemisphere, and it is good in the Southern Hemisphere except above the Antarctic region. The datasets do not agree as well with respect to the horizontal mixing term, especially in the Northern Hemisphere where horizontal mixing has a smaller contribution in WACCM than in the reanalyses. WACCM is investigated through three model realizations and a sensitivity test using the previous version of the gravity wave parameterization. The internal variability of the horizontal mixing in WACCM is large in the polar regions and is comparable to the differences between the dynamical reanalyses. The sensitivity test has a relatively small impact on the horizontal mixing term, but it significantly changes the vertical advection term and produces a less realistic N2O annual cycle above the Antarctic. In this region, all reanalyses show a large wintertime N2O decrease, which is mainly due to horizontal mixing. This is not seen with WACCM, where the horizontal mixing term barely contributes to the TEM budget. While we must use caution in the interpretation of the differences in this region (where the reanalyses show large residuals of the TEM budget), they could be due to the fact that the polar jet is stronger and is not tilted equatorward in WACCM compared with the reanalyses. We also compare the interannual variability in the horizontal mixing and the vertical advection terms between the different datasets. As expected, the horizontal mixing term presents a large variability during austral fall and boreal winter in the polar regions. In the tropics, the interannual variability of the vertical advection term is much smaller in WACCM and JRA-55 than in the other experiments. The large residual in the reanalyses and the disagreement between WACCM and the reanalyses in the Antarctic region highlight the need for further investigations on the modeling of transport in this region of the stratosphere.

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.

The Brewer-Dobson Circulation (BDC) plays a major role in the stratospheric dynamics in terms of tracer transport through the mean residual meridional advection and the isentropic 2-way mixing. The climatological BDC in the Whole Atmosphere Community Climate Model (WACCM) is separated in its components and evaluated through a comparison with a chemical reanalysis of the Aura Microwave Limb Sounder version 2 (BRAM2) and with a chemistry-transport model driven by four modern reanalyses (ERA-Interim, JRA-55, MERRA and MERRA2). The BDC seasonal means and climatological annual cycle are addressed using the Transformed Eulerian Mean (TEM) analysis of the long-lived tracer N2O. The N2O TEM budget terms considered in this study are the vertical residual advection and the horizontal two-way mixing terms.WACCM presents a general underestimation of the horizontal mixing term in the wintertime Northern Hemisphere with respect to the reanalyses throughout the stratosphere.In the wintertime antarctic region the mid-low stratospheric horizontal mixing term in WACCM does not agree with the reanalyses: it shows near-zero positive values, while all the reanalyses show a consistent negative contribution. This disagreement between WACCM and the reanalyses is located in the region and period of the polar vortex development, and can be related to a different representation of the polar jet. In this region the reanalyses are nevertheless affected by large uncertanties of the TEM analysis: the residual term of the budget has the same magnitude as the horizontal mixing term.Even though the residual term can be interpreted as the effect of sub-grid mixing processes, caution must be exerted when considering these regions because the N2O TEM budget is not completetely closed.The mid-stratospheric arctic region are characterized by smaller uncertanties of the TEM budget together with large differences among the datasets during winter: the WACCM realizations, characterized by a large internal variability, show a smaller horizontal mixing contribution with respect to the reanalyses. The agreement among datasets is generally improved when considering the middle and low latitudes, especially in the Northern Hemisphere: those regions are characterized by smaller differences among datasets and a well-closed TEM budget.The inter-annual variability of the horizontal mixing term and the vertical advection term is highly latitude-dependent: the horizontal mixing term presents a large variability, together with a large dataset spread, in the antarctic region in the austral fall and during boreal winter in the Arctic; the vertical advection shows large variability in the arctic region and large model spread in the Tropical regions.

Africa experiences a fast urban inhabitants growth, caused by the largest population boom in the world, combined with rural exodus. Many cities are heavily affected by air pollution. It is therefore essential to monitor the concentrations of the various polluting species such as NO2, HCHO, O3 and aerosols, which have a direct impact on the population health. The sources of pollutant in Africa are different from those found in Europe. For example, forest fires and household cooking largely contribute to the NO2 and HCHO burdens in Central Africa. However, many large African cities, such as the City of Kinshasa, capital of the Democratic Republic of Congo, do not have atmospheric measurement instruments.In order to tackle the lack of measurements in Kinshasa, the Royal Belgian Institute of Space Aeronomy (BIRA-IASB) has, in collaboration with the University of Kinshasa (UniKin), installed an optical remote sensing instrument on the UniKin site (-4.42°S, 15.31°E). Installed in May 2017, the instrument has been in operation until today and provides data to measure the column amounts of several polluting species in the atmosphere of Kinshasa. The instrument is based on a compact AVANTES spectrometer covering the spectral range 290 - 450 nm with 0.7 nm resolution. The spectrometer is a Czerny-Turner type with an entry slit of 50 μm wide, and an array of 1200 l/mm. A 10 m long and 600 μm diameter optical fiber is connected to the spectrometer to receive the incident light beam from the sky. Measurements were mainly made by looking in a fixed direction until November 2019. Since then, a Multi-Axis geometry (MAX-DOAS) has been implemented.The measurements provided by this DOAS instrument allowed us to start studying the atmosphere of Kinshasa using the QDOAS software, which allows us to find the oblique columns of different observed species. This poster will present the instrument, the database and the procedure used to convert these oblique columns into vertical columns, using the air mass factors calculated with the radiative transfer model. We also present our first MAX-DOAS results, analyzed using the retrieval tools of the ESA FRM4DOAS project. The study of current results clearly shows the signature of polluting species such as NO2, HCHO in the atmosphere of Kinshasa. We also use simulations by the GEOS-Chem chemistry transport model to evaluate the magnitude of the emissions needed to explain the observed column amounts. These observations made in Kinshasa could contribute to the validation of satellite products and the refinement of models. We present a first comparison of Kinshasa's ground-based observations with those of the OMI and TROPOMI satellites

Water vapour in the atmosphere is not only a strong greenhouse gas, but also affects many atmospheric processes such as the formation of clouds and precipitation. With increasing temperature, Integrated Water Vapour (IWV) is expected to increase. Analysing how atmospheric water vapour changes in time is therefore important to monitor ongoing climate change. To determine whether IWV increases in Switzerland as expected, we asses IWV trends from a tropospheric water radiometer (TROWARA) in Bern, from a Fourier transform infrared (FTIR) spectrometer at Jungfraujoch and from the Swiss network of ground-based Global Navigation Satellite System (GNSS) stations. In addition, trends are assessed from reanalysis data, using the European Centre for Medium-Range Weather Forecasts (ECMWF) reanalysis (ERA5) and the Modern-Era Retrospecitve Analysis for Research and Applications (MERRA-2). Ground-based GNSS data are well suited for IWV trends due to their high temporal resolution and the spatially dense networks. However, they are highly sensitvie to instrumental changes and care has to be taken when determining GNSS based trends. We therefore use a straightforward trend method to account for jumps in the GNSS data when instrumental changes were performed. Our data show mostly positive IWV trends between 2 and 5% per decade in Switzerland. GNSS trends are significant for some stations and the significance has the tendency to increase with altitude. Further, we found that IWV scales on average to lower tropospheric temperatures as expected, except in winter. However, the correlation between IWV and temperature based on reanalysis data is spatially incoherent. Besides our positive IWV trends, we found a good agreement of radiometer, GNSS and reanalysis data in Bern. Further, we found a dry bias of the FTIR compared to GNSS data at Jungfraujoch, due to the restriction of FTIR to clear-sky conditions. Our results are generally consistent with the positive water vapour feedback in a warming climate. We show that ground-based GNSS networks provide a valuable source for regional climate monitoring with high spatial and temporal resolution, but homogeneously reprocessed data and advanced trend techniques are needed to account for data jumps.

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 &pm; 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 (&pm; 0.05) × 1015+ 0.64 (&pm; 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.

Formic (HCOOH) and acetic acids (CH3COOH) are the most abundant carboxylic acids in the Earth's atmosphere and key compounds to aqueous-phase chemistry. Here we present the first distributions of CH3COOH retrieved from the 2007–2018 satellite observations of the nadir-looking infrared atmospheric sounding interferometer (IASI), using a neural network-based retrieval approach. A joint analysis with the IASI HCOOH product reveals that the two species exhibit similar distributions, seasonality, and atmospheric burden, pointing to major common sources. We show that their abundance is highly correlated to isoprene and monoterpenes emissions, as well as to biomass burning. Over Africa, evidence is provided that residual smoldering combustion might be a major driver of the HCOOH and CH3COOH seasonality. Earlier seasonal enhancement of HCOOH at Northern Hemisphere middle and high latitudes and late seasonal secondary peaks of CH3COOH in the tropics suggest that sources and production pathways specific to each species are also at play., SCOPUS: ar.j, info:eu-repo/semantics/published

We analyzed seasonality and interannual variability of tropospheric HCN column amounts in densely populated eastern China for the first time. The results were derived from solar absorption spectra recorded with ground-based high spectral resolution Fourier transform infrared (FTIR) spectrometer at Hefei (117°10′ E, 31°54′ N) between 2015 and 2018. The tropospheric HCN columns over Hefei, China showed significant seasonal variations with three monthly mean peaks throughout the year. The magnitude of the tropospheric HCN column peak in May > September > December. The tropospheric HCN column reached a maximum of (9.8 ± 0.78) × 1015 molecules/cm2 in May and a minimum of (7.16 ± 0.75) × 1015 molecules/cm2 in November. In most cases, the tropospheric HCN columns at Hefei (32° N) are higher than the FTIR observations at Ny Alesund (79° N), Kiruna (68° N), Bremen (53° N), Jungfraujoch (47° N), Toronto (44° N), Rikubetsu (43° N), Izana (28° N), Mauna Loa (20° N), La Reunion Maido (21° S), Lauder (45° S), and Arrival Heights (78° S) that are affiliated with the Network for Detection of Atmospheric Composition Change (NDACC). Enhancements of the tropospheric HCN columns were observed between September 2015 and July 2016 compared to the counterpart measurements in other years. The magnitude of the enhancement ranges from 5 to 46 % with an average of 22 %. Enhancement of tropospheric HCN (ΔHCN) is correlated with the coincident enhancement of tropospheric CO (ΔCO), indicating that enhancements of tropospheric CO and HCN were due to the same sources. The GEOS-Chem tagged CO simulation, the global fire maps and the PSCFs (Potential Source Contribution Function) calculated using back trajectories revealed that the seasonal maxima in May is largely due to the influence of biomass burning in South Eastern Asia (SEAS) (41 ± 13.1 %), Europe and Boreal Asia (EUBA) (21 ± 9.3 %) and Africa (AF) (22 ± 4.7 %). The seasonal maxima in September is largely due to the influence of biomass burnings in EUBA (38 ± 11.3 %), AF (26 ± 6.7 %), SEAS (14 ± 3.3 %), and Northern America (NA) (13.8 ± 8.4 %). For the seasonal maxima in December, dominant contributions are from AF (36 ± 7.1 %), EUBA (21 ± 5.2 %), and NA (18.7 ± 5.2 %). The tropospheric HCN enhancement between September 2015 and July 2016 at Hefei (32° N) were attributed to an elevated influence of biomass burnings in SEAS, EUBA, and Oceania (OCE) in this period. Particularly, an elevated fire number in OCE in the second half of 2015 dominated the tropospheric HCN enhancement in September–December 2015. An elevated fire number in SEAS in the first half of 2016 dominated the tropospheric HCN enhancement in January–July 2016.

Vertically integrated water vapour (IWV) is expected to increase globally in a warming climate. To determine whether IWV increases as expected on a regional scale, we present IWV trends in Switzerland from ground-based remote sensing techniques and reanalysis models, considering data for the time period 1995 to 2018. We estimate IWV trends from a ground-based microwave radiometer in Bern, from a Fourier transform infrared (FTIR) spectrometer at Jungfraujoch, from reanalysis data (ERA5 and MERRA-2) and from Swiss ground-based Global Navigation Satellite System (GNSS) stations. Using a straightforward trend method, we account for jumps in the GNSS data, which are highly sensitive to instrumental changes. We found that IWV generally increased by 2 % per decade to 5 % per decade, with deviating trends at some GNSS stations. Trends were significantly positive at 17 % of all GNSS stations, which often lie at higher altitudes (between 850 and 1650 m above sea level). Our results further show that IWV in Bern scales to air temperature as expected (except in winter), but the IWV–temperature relation based on reanalysis data in the whole of Switzerland is not clear everywhere. In addition to our positive IWV trends, we found that the radiometer in Bern agrees within 5 % with GNSS and reanalyses. At the Jungfraujoch high-altitude station, we found a mean difference of 0.26 mm (15 %) between the FTIR and coincident GNSS data, improving to 4 % after an antenna update in 2016. In general, we showed that ground-based GNSS data are highly valuable for climate monitoring, given that the data have been homogeneously reprocessed and that instrumental changes are accounted for. We found a response of IWV to rising temperature in Switzerland, which is relevant for projected changes in local cloud and precipitation processes.

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.

Atmospheric carbon monoxide (CO) and methane ( CH4 ) mole fractions are measured by ground-based in situ cavity ring-down spectroscopy (CRDS) analyzers and Fourier transform infrared (FTIR) spectrometers at two sites (St Denis and Maido) on Reunion Island (21 ∘ S, 55 ∘ E) in the Indian Ocean. Currently, the FTIR Bruker IFS 125HR at St Denis records the direct solar spectra in the near-infrared range, contributing to the Total Carbon Column Observing Network (TCCON). The FTIR Bruker IFS 125HR at Maido records the direct solar spectra in the mid-infrared (MIR) range, contributing to the Network for the Detection of Atmospheric Composition Change (NDACC). In order to understand the atmospheric CO and CH4 variability on Reunion Island, the time series and seasonal cycles of CO and CH4 from in situ and FTIR (NDACC and TCCON) measurements are analyzed. Meanwhile, the difference between the in situ and FTIR measurements are discussed. The CO seasonal cycles observed from the in situ measurements at Maido and FTIR retrievals at both St Denis and Maido are in good agreement with a peak in September–November, primarily driven by the emissions from biomass burning in Africa and South America. The dry-air column averaged mole fraction of CO ( XCO ) derived from the FTIR MIR spectra (NDACC) is about 15.7 ppb larger than the CO mole fraction near the surface at Maido, because the air in the lower troposphere mainly comes from the Indian Ocean while the air in the middle and upper troposphere mainly comes from Africa and South America. The trend for CO on Reunion Island is unclear during the 2011–2017 period, and more data need to be collected to get a robust result. A very good agreement is observed in the tropospheric and stratospheric CH4 seasonal cycles between FTIR (NDACC and TCCON) measurements, and in situ and the Michelson Interferometer for Passive Atmospheric Sounding (MIPAS) satellite measurements, respectively. In the troposphere, the CH4 mole fraction is high in August–September and low in December–January, which is due to the OH seasonal variation. In the stratosphere, the CH4 mole fraction has its maximum in March–April and its minimum in August–October, which is dominated by vertical transport. In addition, the different CH4 mole fractions between the in situ, NDACC and TCCON CH4 measurements in the troposphere are discussed, and all measurements are in good agreement with the GEOS-Chem model simulation. The trend of X CH 4 is 7.6±0.4 ppb yr −1 from the TCCON measurements over the 2011 to 2017 time period, which is consistent with the CH4 trend of 7.4±0.5 ppb yr −1 from the in situ measurements for the same time period at St Denis.

Carbonyl sulfide (OCS) provides a proxy for measuring photosynthesis and is the primary background source of stratospheric aerosols. OCS emissions due to biomass burning are a variable and substantial (over 10%) part of the current OCS budget. OCS emission ratios from open burning fires, coupled with 1997–2016 data from the Global Fire Emissions Database (GFED4), yield OCS biomass burning emissions with a global average annual flux of 60 ± 37 Gg(S) year⁻¹. A global box model suggests these emissions are more consistent with observations from global atmospheric composition monitoring networks than fluxes derived from previous synthesis papers. Even after considering the uncertainty in emission factor observations for each category of emissions and the interannual variation in total burned dry matter, the total OCS emissions from open burning are insufficient to account for the large imbalance between current estimates of global OCS sources and sinks.

SF6 total columns were successfully retrieved from FTIR (Fourier transform infrared) measurements (Saint Denis and Maido) on Reunion Island (21 ∘ S, 55 ∘ E) between 2004 and 2016 using the SFIT4 algorithm: the retrieval strategy and the error budget were presented. The FTIR SF6 retrieval has independent information in only one individual layer, covering the whole of the troposphere and the lower stratosphere. The trend in SF6 was analysed based on the FTIR-retrieved dry-air column-averaged mole fractions ( X SF 6 ) on Reunion Island, the in situ measurements at America Samoa (SMO) and the collocated satellite measurements (Michelson Interferometer for Passive Atmospheric Sounding, MIPAS, and Atmospheric Chemistry Experiment Fourier Transform Spectrometer, ACE-FTS) in the southern tropics. The SF6 annual growth rate from FTIR retrievals is 0.265±0.013 pptv year−1 for 2004–2016, which is slightly weaker than that from the SMO in situ measurements ( 0.285±0.002 pptv year−1 ) for the same time period. The SF6 trend in the troposphere from MIPAS and ACE-FTS observations is also close to the ones from the FTIR retrievals and the SMO in situ measurements.

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.

In this paper, we present an optimized retrieval strategy for carbonyl sulfide (OCS), using Fourier transform infrared (FTIR) solar observations made at the high-altitude Jungfraujoch station in the Swiss Alps. More than 200 lines of the ν3 fundamental band of OCS have been systematically evaluated and we selected 4 microwindows on the basis of objective criteria minimizing the effect of interferences, mainly by solar features, carbon dioxide and water vapor absorption lines, while maximizing the information content. Implementation of this new retrieval strategy provided an extended time series of the OCS abundance spanning the 1995–2015 time period, for the study of the long-term trend and seasonal variation of OCS in the free troposphere and stratosphere. Three distinct periods characterize the evolution of the tropospheric partial columns: a first decreasing period (1995–2002), an intermediate increasing period (2002–2008), and the more recent period (2008–2015) which shows no significant trend. Our FTIR tropospheric and stratospheric time series are compared with new in situ gas chromatography mass spectrometry (GCMS) measurements performed by Empa (Laboratory for Air Pollution/Environmental Technology) at the Jungfraujoch since 2008, and with space-borne solar occultation observations by the ACE-FTS instrument on-board the SCISAT satellite, respectively, and they show good agreement. The OCS signal recorded above Jungfraujoch appears to be closely related to anthropogenic sulfur emissions.

We have developed an approach for retrieving HCFC-142b (CH3CClF2) from ground-based high-resolution infrared solar spectra, using its ν7 band Q branch in the 900–906 cm−1 interval. Interferences by HNO3, CO2 and H2O have to be accounted for. Application of this approach to observations recorded within the framework of long-term monitoring activities carried out at the northern mid-latitude, high-altitude Jungfraujoch station in Switzerland (46.5°N, 8.0°E, 3580 m above sea level) has provided a total column times series spanning the 1989 to mid-2015 time period. A fit to the HCFC-142b daily mean total column time series shows a statistically-significant long-term trend of (1.23±0.08×1013 molec cm−2) per year from 2000 to 2010, at the 2-σ confidence level. This corresponds to a significant atmospheric accumulation of (0.94±0.06) ppt (1 ppt=1/1012) per year for the mean tropospheric mixing ratio, at the 2−σ confidence level. Over the subsequent time period (2010–2014), we note a significant slowing down in the HCFC-142b buildup. Our ground-based FTIR (Fourier Transform Infrared) results are compared with relevant data sets derived from surface in situ measurements at the Mace Head and Jungfraujoch sites of the AGAGE (Advanced Global Atmospheric Gases Experiment) network and from occultation measurements by the ACE-FTS (Atmospheric Chemistry Experiment-Fourier Transform Spectrometer) instrument on-board the SCISAT satellite.

We present a multi-year time series of column abundances of carbon monoxide (CO), hydrogen cyanide (HCN), and ethane (C2H6) measured using Fourier transform infrared (FTIR) spectrometers at ten sites affiliated with the Network for Detection of Atmospheric Composition Change (NDACC). Six are high-latitude sites: Eureka, Ny-Alesund, Thule, Kiruna, Poker Flat, and St. Petersburg , and four are mid-latitude sites: Zugspitze, Jungfraujoch, Toronto, and Rikubetsu. For each site, the inter-annual trends and seasonal variabilities of the CO time series are accounted for, allowing ambient concentrations to be determined. Enhancements above ambient levels were used to identify possible wildfire pollution events. Since the abundance of each trace gas emitted in a wildfire event is specific to the type of vegetation burned and the burning phase, correlations of CO to the long-lived wildfire tracers HCN and C2H6 allow for further confirmation of the detection of wildfire pollution, while complementary measurements of aerosol optical depth from nearby AERONET sites confirm the presence of wildfire smoke. A GEOS-Chem tagged CO simulation with Global Fire Assimilation System (GFAS) biomass burning emissions was used to determine the source attribution of CO concentrations at each site from 2003–2018. The influence of the various wildfire sources is found to differ between sites while North American and Asian boreal wildfires fires were found to be the greatest contributors to episodic CO enhancements in the summertime at all sites.