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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.

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.

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...

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.

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

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.

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.

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.

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.

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.

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.

Uncertainties of tropical methane concentrations, retrieved from spectra recorded by the Michelson Interferometer for Passive Atmospheric Sounding (MIPAS), MIPAS version V5R_CH4_220 are large. We explore the relation of these uncertainties with water vapour variability. We further show that these uncertainties have been reduced in MIPAS version V5R_CH4_224. Coincident measurements of CH4 by MIPAS, ground based FTIR and CH4 derived from EOS MLS coincident measurements of atmospheric water vapour (H2O), carbon monoxide (CO) and nitrous oxide (N2O) are used to estimate the standard uncertainty of MIPAS CH4 220, MIPAS CH4 224 and natural variability of H2O. Different methods such as bias evaluation, differential method and correlation coefficient are employed to explore the latitudinal variations of standard uncertainty of MIPAS CH4 220 and natural variability of water vapour as well as its reduction on MIPAS CH4 224. The averaged bias between MIPAS CH4 220 and ground-based FTIR measurements are −12.3 %, 8.4 % and 1.2 % for tropics, mid-latitudes and high latitudes, respectively. The standard deviations of the differences for these latitudinal bands are 5.9 %, 4.8 % and 4.7 %. More-over, the correlation coefficient between MIPAS CH4 220 and MIPAS V5R_N2O_220 is 0.32 in the upper troposphere and lower stratosphere over tropics and larger than the mod-est value 0.5 in mid and high latitudes. The poor correlation between MIPAS CH4 220 and MIPAS N2O 220 over tropics can indicate the large uncertainty of MIPAS CH4 220 over tropics that is related to water variability. Similarly, mean relative difference between MIPAS CH4 224 and ground-based FTIR measurements are 3.9 %, −2.6 % and −2.7 % in altitude 15–21 km and the average estimated uncertainty of MIPAS CH4 224 methane were obtained 2.4 %, 1.4 % and 5.1 % in altitude ranges of 15 to 27 km for tropics, mid and high latitudes, respectively. The estimated measurement uncertainty of MIPAS CH4 224 is different for the three latitude bands in the northern hemisphere, reflecting the latitudinal variation of uncertainties of MIPAS methane. However, the large reduction of uncertainty in MIPAS CH4 224 as com-pared to MIPAS CH4 220 has been confirmed for the tropical measurements. The correlation coefficients between the uncertainty of MIPAS CH4 220 and the variability of water vapour in lower stratosphere are strong (0.88) on monthly temporal scales. Similar methods were used for MIPAS CH4 224. It was found that the uncertainty in methane due to the variability of water vapor has been reduced.

Knowing the spatial and seasonal distributions of nitric acid (HNO3) around the globe is of great interest and allows us to comprehend the processes regulating stratospheric ozone, especially in the polar regions. Due to its unprecedented spatial and temporal sampling, the nadir-viewing Infrared Atmospheric Sounding Interferometer (IASI) is capable of sounding the atmosphere twice a day globally, with good spectral resolution and low noise. With the Fast Optimal Retrievals on Layers for IASI (FORLI) algorithm, we are retrieving, in near real time, columns as well as vertical profiles of several atmospheric species, among which is HNO3. We present in this paper the first characterization of the FORLI-HNO3 profile products, in terms of vertical sensitivity and error budgets. We show that the sensitivity of IASI to HNO3 is highest in the lower stratosphere (10–20 km), where the largest amounts of HNO3 are found, but that the vertical sensitivity of IASI only allows one level of information on the profile (degrees of freedom for signal, DOFS; ∼ 1). The sensitivity near the surface is negligible in most cases, and for this reason, a partial column (5–35 km) is used for the analyses. Both vertical profiles and partial columns are compared to FTIR ground-based measurements from the Network for the Detection of Atmospheric Composition Change (NDACC) to characterize the accuracy and precision of the FORLI-HNO3 product. The profile validation is conducted through the smoothing of the raw FTIR profiles by the IASI averaging kernels and gives good results, with a slight overestimation of IASI measurements in the upper troposphere/lower stratosphere (UTLS) at the six chosen stations (Thule, Kiruna, Jungfraujoch, Izaña, Lauder and Arrival Heights). The validation of the partial columns (5–35 km) is also conclusive with a mean correlation of 0.93 between IASI and the FTIR measurements. An initial survey of the HNO3 spatial and seasonal variabilities obtained from IASI measurements for a 1-year (2011) data set shows that the expected latitudinal gradient of concentrations from low to high latitudes and the large seasonal variability in polar regions (cycle amplitude around 30 % of the seasonal signal, peak to peak) are well represented by IASI data.

This paper studies the seasonal variation of surface and column CO at three different sites (Paris, Jungfraujoch and Wollongong), with an emphasis on establishing a link between the CO vertical distribution and the nature of CO emission sources. We find the first evidence of a time lag between surface and free tropospheric CO seasonal variations in the Northern Hemisphere. The CO seasonal variability obtained from the total columns and free tropospheric partial columns shows a maximum around March-April and a minimum around September-October in the Northern Hemisphere (Paris and Jungfraujoch). In the Southern Hemisphere (Wollongong) this seasonal variability is shifted by about 6 months. Satellite observations by the IASI-MetOp (Infrared Atmospheric Sounding Interferometer) and MOPITT (Measurements Of Pollution In The Troposphere) instruments confirm this seasonality. Ground-based FTIR (Fourier transform infrared) measurements provide useful complementary information due to good sensitivity in the boundary layer. In situ surface measurements of CO volume mixing ratios at the Paris and Jungfraujoch sites reveal a time lag of the near-surface seasonal variability of about 2 months with respect to the total column variability at the same sites. The chemical transport model GEOS-Chem (Goddard Earth Observing System chemical transport model) is employed to interpret our observations. GEOS-Chem sensitivity runs identify the emission sources influencing the seasonal variation of CO. At both Paris and Jungfraujoch, the surface seasonality is mainly driven by anthropogenic emissions, while the total column seasonality is also controlled by air masses transported from distant sources. At Wollongong, where the CO seasonality is mainly affected by biomass burning, no time shift is observed between surface measurements and total column data., SCOPUS: ar.j, info:eu-repo/semantics/published

Only very few long-term records of formaldehyde (HCHO) exist that are suitable for trend analysis. Furthermore, many uncertainties remain as to its diurnal cycle, representing a large short-term variability superimposed on seasonal and inter-annual variations that should be accounted for when comparing ground-based observations to, e.g., model results. In this study, we derive a multi-decadal time series (January 1988–June 2015) of HCHO total columns from ground-based high-resolution Fourier transform infrared (FTIR) solar spectra recorded at the high-altitude station of Jungfraujoch (Swiss Alps, 46.5° N, 8.0° E, 3580 m a. s. l. ), allowing for the characterization of the mid-latitudinal atmosphere for background conditions. First we investigate the HCHO diurnal variation, peaking around noontime and mainly driven by the intra-day insolation modulation and methane (CH4) oxidation. We also characterize quantitatively the diurnal cycles by adjusting a parametric model to the observations, which links the daytime to the HCHO columns according to the monthly intra-day regimes. It is then employed to scale all the individual FTIR measurements on a given daytime in order to remove the effect of the intra-day modulation for improving the trend determination and the comparison with HCHO columns simulated by the state-of-the-art GEOS-Chem v9-02 chemical transport model. Such a parametric model will be useful to scale the Jungfraujoch HCHO columns on satellite overpass times in the framework of future calibration/validation efforts of space-borne sensors. GEOS-Chem sensitivity tests suggest then that the seasonal and inter-annual HCHO column variations above Jungfraujoch are predominantly led by the atmospheric CH4 oxidation, with a maximum contribution of 25 % from the anthropogenic non-methane volatile organic compound precursors during wintertime. Finally, trend analysis of the so-scaled 27-year FTIR time series reveals a long-term evolution of the HCHO columns in the remote troposphere to be related to the atmospheric CH4 fluctuations and the short-term OH variability: +2.9 % year−1 between 1988 and 1995, −3.7 % year−1 over 1996–2002 and +0.8 % year−1 from 2003 onwards.

Measurements of the atmospheric HDO/H2O ratio help us to better understand the hydrological cycle and improve models to correctly simulate tropospheric humidity and therefore climate change. We present an updated version of the column-averaged HDO/H2O ratio data set from the SCanning Imaging Absorption spectroMeter for Atmospheric CHartographY (SCIAMACHY). The data set is extended with 2 additional years, now covering 2003–2007, and is validated against co-located ground-based total column δD measurements from Fourier transform spectrometers (FTS) of the Total Carbon Column Observing Network (TCCON) and the Network for the Detection of Atmospheric Composition Change (NDACC, produced within the framework of the MUSICA project). Even though the time overlap among the available data is not yet ideal, we determined a mean negative bias in SCIAMACHY δD of −35 ± 30‰ compared to TCCON and −69 ± 15‰ compared to MUSICA (the uncertainty indicating the station-to-station standard deviation). The bias shows a latitudinal dependency, being largest (∼ −60 to −80‰) at the highest latitudes and smallest (∼ −20 to −30‰) at the lowest latitudes. We have tested the impact of an offset correction to the SCIAMACHY HDO and H2O columns. This correction leads to a humidity- and latitude-dependent shift in δD and an improvement of the bias by 27‰, although it does not lead to an improved correlation with the FTS measurements nor to a strong reduction of the latitudinal dependency of the bias. The correction might be an improvement for dry, high-altitude areas, such as the Tibetan Plateau and the Andes region. For these areas, however, validation is currently impossible due to a lack of ground stations. The mean standard deviation of single-sounding SCIAMACHY–FTS differences is ∼ 115‰, which is reduced by a factor ∼ 2 when we consider monthly means. When we relax the strict matching of individual measurements and focus on the mean seasonalities using all available FTS data, we find that the correlation coefficients between SCIAMACHY and the FTS networks improve from 0.2 to 0.7–0.8. Certain ground stations show a clear asymmetry in δD during the transition from the dry to the wet season and back, which is also detected by SCIAMACHY. This asymmetry points to a transition in the source region temperature or location of the water vapour and shows the added information that HDO/H2O measurements provide when used in combination with variations in humidity.

An improved nitrogen dioxide (NO2) slant column density retrieval for the Ozone Monitoring Instrument (OMI) in the 405–465 nm spectral region is presented. Since the launch of OMI on board NASA's EOS-Aura satellite in 2004, differential optical absorption spectroscopy (DOAS) retrievals of NO2 slant column densities have been the starting point for the KNMI DOMINO and NASA SP NO2 vertical column data as well as the OMI NO2 data of some other institutes. However, recent intercomparisons between NO2 retrievals from OMI and other UV/Vis and limb spectrometers, as well as ground-based measurements, suggest that OMI stratospheric NO2 is biased high. This study revises and, for the first time, fully documents the OMI NO2 retrieval in detail. The representation of the OMI slit function to convolve high-resolution reference spectra onto the relevant spectral grid is improved. The window used for the wavelength calibration is optimised, leading to much-reduced fitting errors. Ozone and water vapour spectra used in the fit are updated, reflecting the recently improved knowledge of their absorption cross section in the literature. The improved spectral fit also accounts for absorption by the O2–O2 collision complex and by liquid water over clear-water areas. The main changes in the improved spectral fitting result from the updates related to the wavelength calibration: the RMS error of the fit is reduced by 23% and the NO2 slant column by 0.85 × 1015 molec cm−2, independent of latitude, solar zenith angle and NO2 value. Including O2–O2 and liquid water absorption and updating the O3 and water vapour cross-section spectra further reduces NO2 slant columns on average by 0.35 × 1015 molec cm−2, accompanied by a further 9% reduction in the RMS error of the fit. The improved OMI NO2 slant columns are consistent with independent NO2 retrievals from other instruments to within a range that can be explained by photochemically driven diurnal increases in stratospheric NO2 and by small differences in fitting window and approach. The revisions indicate that current OMI NO2 slant columns suffered mostly from an additive positive offset, which is removed by the improved wavelength calibration and representation of the OMI slit function. It is therefore anticipated that the improved NO2 slant columns are most important to retrievals of spatially homogeneous stratospheric NO2 rather than to heterogeneous tropospheric NO2.

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.

Methanol (CH3OH) is the second most abundant organic compound in the Earth's atmosphere after methane. In this study, we present the first long-term time series of methanol total, lower tropospheric and upper tropospheric–lower stratospheric partial columns derived from the analysis of high resolution Fourier transform infrared solar spectra recorded at the Jungfraujoch station (46.5° N, 3580 m a.s.l.). The retrieval of methanol is very challenging due to strong absorptions of ozone in the region of the selected υ8 band of CH3OH. Two wide spectral intervals have been defined and adjusted in order to maximise the information content. Methanol does not exhibit a significant trend over the 1995–2012 time period, but a strong seasonal modulation characterised by maximum values and variability in June–July, minimum columns in winter and a peak-to-peak amplitude of 130%. Analysis and comparisons with in situ measurements carried out at the Jungfraujoch and ACE-FTS (Atmospheric Chemistry Experiment-Fourier transform spectrometer) occultations have been performed. The total and lower tropospheric columns are also compared with IMAGESv2 model simulations. There is no systematic bias between the observations and IMAGESv2 but the model underestimates the peak-to-peak amplitude of the seasonal modulations.

The Measurements of Pollution in the Troposphere (MOPITT) satellite instrument provides the longest continuous dataset of carbon monoxide (CO) from space. We perform the first validation of MOPITT version 6 retrievals using total column CO measurements from ground-based remote-sensing Fourier transform infrared spectrometers (FTSs). Validation uses data recorded at 14 stations, that span a wide range of latitudes (80° N to 78° S), in the Network for the Detection of Atmospheric Composition Change (NDACC). MOPITT measurements are spatially co-located with each station, and different vertical sensitivities between instruments are accounted for by using MOPITT averaging kernels (AKs). All three MOPITT retrieval types are analyzed: thermal infrared (TIR-only), joint thermal and near infrared (TIR–NIR), and near infrared (NIR-only). Generally, MOPITT measurements overestimate CO relative to FTS measurements, but the bias is typically less than 10 %. Mean bias is 2.4 % for TIR-only, 5.1 % for TIR–NIR, and 6.5 % for NIR-only. The TIR–NIR and NIR-only products consistently produce a larger bias and lower correlation than the TIR-only. Validation performance of MOPITT for TIR-only and TIR–NIR retrievals over land or water scenes is equivalent. The four MOPITT detector element pixels are validated separately to account for their different uncertainty characteristics. Pixel 1 produces the highest standard deviation and lowest correlation for all three MOPITT products. However, for TIR-only and TIR–NIR, the error-weighted average that includes all four pixels often provides the best correlation, indicating compensating pixel biases and well-captured error characteristics. We find that MOPITT bias does not depend on latitude but rather is influenced by the proximity to rapidly changing atmospheric CO. MOPITT bias drift has been bound geographically to within ±0.5 % yr−1 or lower at almost all locations.

The long term trend of the atmospheric carbon tetrachloride (CCl4) burden has been retrieved from high spectral resolution infrared solar absorption spectra recorded between January 1999 and June 2011. The observations were made with a Fourier transform spectrometer at the northern mid latitude high altitude Jungfraujoch station in Switzerland (46.5 degrees N latitude 8.0 degrees E longitude 3580 m altitude). Total columns were derived from spectrometric analysis of the strong CCl4 nu(3) band at 794 cm( 1) accounting for all interfering molecules (e.g. H2O CO2 O 3 and a dozen weakly absorbing gases). A significant improvement in the fitting residuals and in the retrieved CCl4 columns was obtained by taking into account line mixing in a strong interfering CO2 Q branch. This procedure had never been implemented in remote sensing CCl4 retrievals though its importance was noted in earlier studies. A fit to the CCl4 daily mean total column time series returns a statistically significant long term trend of ( 1.49 +/ 0.08 x 10(13) mol/cm(2))/yr 2 sigma. This corresponds to an annual decrease of ( 1.31 +/ 0.07) pptv for the mean free tropospheric volume mixing ratio. Furthermore the total column data set reveals a weak seasonal cycle with a peak to peak amplitude of 4.5 with minimum and maximum values occurring in mid February and mid September respectively. This small seasonal modulation is attributed primarily to the residual influence of tropopause height changes throughout the year. The negative trend of the CCl4 loading reflects the continued impact of the regulations implemented by the Montreal Protocol and its strengthening amendments and adjustments. Despite this statistically significant decrease the CCl4 molecule currently remains an important contributor to the atmospheric chlorine budget and thus deserves further monitoring to ensure continued compliance with these strengthenings globally. Our present findings are briefly discussed with respect to recent relevant CCl4 investigations at the ground and from space. (C) 2012 Elsevier Ltd. All rights reserved.

We use the GEOS-Chem global 3-D chemistry transport model to investigate the relative importance of chemical and physical processes that determine observed variability of hydrogen cyanide (HCN) in the troposphere and lower stratosphere. Consequently, we reconcile ground-based FTIR column measurements of HCN, which show annual and semi-annual variations, with recent space-borne measurements of HCN mixing ratio in the tropical lower stratosphere, which show a large two-year variation. We find that the observed column variability over the ground-based stations is determined by a superposition of HCN from several regional burning sources, with GEOS-Chem reproducing these column data with a positive bias of 5%. GEOS-Chem reproduces the observed HCN mixing ratio from the Microwave Limb Sounder and the Atmospheric Chemistry Experiment satellite instruments with a mean negative bias of 20%, and the observed HCN variability with a mean negative bias of 7%. We show that tropical biomass burning emissions explain most of the observed HCN variations in the upper troposphere and lower stratosphere (UTLS), with the remainder due to atmospheric transport and HCN chemistry. In the mid and upper stratosphere, atmospheric dynamics progressively exerts more influence on HCN variations. The extent of temporal overlap between African and other continental burning seasons is key in establishing the apparent bienniel cycle in the UTLS. Similar analysis of other, shorter-lived trace gases have not observed the transition between annual and bienniel cycles in the UTLS probably because the signal of inter-annual variations from surface emission has been diluted before arriving at the lower stratosphere (LS), due to shorter atmospheric lifetimes.

This paper presents extensive validation analyses of ozone observations from the Atmospheric Chemistry Experiment (ACE) satellite instruments: the ACE Fourier Transform Spectrometer (ACE-FTS) and the Measurement of Aerosol Extinction in the Stratosphere and Troposphere Retrieved by Occultation (ACE-MAESTRO) instrument. The ACE satellite instruments operate in the mid-infrared and ultraviolet-visible-near-infrared spectral regions using the solar occultation technique. In order to continue the long-standing record of solar occultation measurements from space, a detailed quality assessment is required to evaluate the ACE data and validate their use for scientific purposes. Here we compare the latest ozone data products from ACE-FTS and ACE-MAESTRO with coincident observations from satellite-borne, airborne, balloon-borne and ground-based instruments, by analysing volume mixing ratio profiles and partial column densities. The ACE-FTS version 2.2 Ozone Update product reports more ozone than most correlative measurements from the upper troposphere to the lower mesosphere. At altitude levels from 16 to 44 km, the mean differences range generally between 0 and +10% with a slight but systematic positive bias (typically +5%). At higher altitudes (45-60 km), the ACE-FTS ozone amounts are significantly larger than those of the comparison instruments by up to ~40% (typically +20%). For the ACE-MAESTRO version 1.2 ozone data product, agreement within ±10% (generally better than ±5%) is found between 18 and 40 km for the sunrise and sunset measurements. At higher altitudes (45-55 km), systematic biases of opposite sign are found between the ACE-MAESTRO sunrise and sunset observations. While ozone amounts derived from the ACE-MAESTRO sunrise occultation data are often smaller than the coincident observations (by as much as -10%), the sunset occultation profiles for ACE-MAESTRO show results that are qualitatively similar to ACE-FTS and indicate a large positive bias (+10 to +30%) in this altitude range. In contrast, there is no significant difference in bias found for the ACE-FTS sunrise and sunset measurements. These systematic effects in the ozone profiles retrieved from the measurements of ACE-FTS and ACE-MAESTRO are being investigated. This work shows that the ACE instruments provide reliable, high quality measurements from the tropopause to the upper stratosphere and can be used with confidence in this vertical domain

The Atmospheric Chemistry Experiment (ACE), also known as SCISAT, was launched on 12 August 2003, carrying two instruments that measure vertical profiles of atmospheric constituents using the solar occultation technique. One of these instruments, the ACE Fourier Transform Spectrometer (ACE-FTS), is measuring volume mixing ratio (VMR) profiles of nitrous oxide (N 2 O) from the upper troposphere to the lower mesosphere at a vertical resolution of about 3–4 km. In this study, the quality of the ACE-FTS version 2.2 N 2 O data is assessed through comparisons with coincident measurements made by other satellite, balloon-borne, aircraft, and ground-based instruments. These consist of vertical profile comparisons with the SMR, MLS, and MIPAS satellite instruments, multiple aircraft flights of ASUR, and single balloon flights of SPIRALE and FIRS-2, and partial column comparisons with a network of ground-based Fourier Transform InfraRed spectrometers (FTIRs). Overall, the quality of the ACE-FTS version 2.2 N 2 O VMR profiles is good over the entire altitude range from 5 to 60 km. Between 6 and 30 km, the mean absolute differences for the satellite comparisons lie between -42 ppbv and +17 ppbv, with most within ±20 ppbv. This corresponds to relative deviations from the mean that are within ±15%, except for comparisons with MIPAS near 30 km, for which they are as large as 22.5%. Between 18 and 30 km, the mean absolute differences are generally within ±10 ppbv, again excluding the aircraft and balloon comparisons. From 30 to 60 km, the mean absolute differences are within ±4 ppbv, and are mostly between -2 and +1 ppbv. Given the small N 2 O VMR in this region, the relative deviations from the mean are therefore large at these altitudes, with most suggesting a negative bias in the ACE-FTS data between 30 and 50 km. In the comparisons with the FTIRs, the mean relative differences between the ACE-FTS and FTIR partial columns are within ±6.6% for eleven of the twelve contributing stations. This mean relative difference is negative at ten stations, suggesting a small negative bias in the ACE-FTS partial columns over the altitude regions compared. Excellent correlation ( R =0.964) is observed between the ACE-FTS and FTIR partial columns, with a slope of 1.01 and an intercept of -0.20 on the line fitted to the data.

The ACE-FTS (Atmospheric Chemistry Experiment – Fourier Transform Spectrometer) solar occultation instrument that was launched onboard the Canadian SCISAT-1 satellite in August 2003 is measuring vertical profiles from the upper troposphere to the lower mesosphere for a large number of atmospheric constituents. Methane is one of the key species. The version v2.2 data of the ACE-FTS CH4 data have been compared to correlative satellite, balloon-borne and ground-based Fourier transform infrared remote sensing data to assess their quality. The comparison results indicate that the accuracy of the data is within 10% in the upper troposphere – lower stratosphere, and within 25% in the middle and higher stratosphere up to the lower mesosphere (

The Institute of Astrophysics of the University of Liège has been present at the High Altitude Research Station Jungfraujoch, Switzerland, since the late 1940s, to perform spectrometric solar observations under dry and weakly polluted high-mountain conditions. Several solar atlases of photometric quality, extending altogether from the near-ultra-violet to the middle-infrared, were produced between 1956 and 1994, first with grating spectrometers then with Fourier transform instruments. During the early 1970s, scientific concerns emerged about atmospheric composition changes likely to set in as a consequence of the growing usage of nitrogen-containing agricultural fertilisers and the industrial production of chlorine-bearing compounds such as the chlorofluorocarbons and hydro-chlorofluorocarbons. Resulting releases to the atmosphere with ensuing photolysis in the stratosphere and catalytic depletion of the protective ozone layer prompted a worldwide consortium of chemical manufacturing companies to solicit the Liège group to help in clarifying these concerns by undertaking specific observations with its existing Jungfraujoch instrumentation. The following pages evoke the main steps that led from quasi full sun-oriented studies to priority investigations of the Earth's atmosphere, in support of both the Montreal and the Kyoto Protocols.

Long-term trend and seasonal variation of the mean free tropospheric volume mixing ratios of carbon monoxide (CO) and hydrogen cyanide (HCN) have been derived from analysis of a time series of solar absorption spectra recorded from the US National Solar Observatory on Kitt Peak (31.9°N, 111.6°W, 2.09 km altitude) spanning almost three decades. The results of a fit to the CO 258 daily averages from May 1977 to April 2005 as a function of time with a model that assumes a sinusoidal seasonal cycle and a linear long-term trend with time yield a mean volume mixing ratio of 102 ± 3 ) parts per billion ( 10 - 9 per unit volume) below 10 km altitude, 1 sigma. The CO measurements show a seasonal cycle with a maximum in March and a minimum in September with an amplitude of ( 22.3 ± 1.5 ) % relative to the mean. The best-fit corresponds to a long-term CO trend of ( 0.15 ± 0.14 ) % yr - 1 , 1 sigma, relative to the mean. To quantify the possible impact of periods of intense fires, the CO measurements have been compared with the measurements of HCN, a well-documented emission product of biomass burning with a lifetime of ∼ 5 months. The best fit to the full HCN time series of 208 daily averages from May 1978 to April 2005 results in a mean volume mixing ratio of ( 0.219 ± 0.007 ) ppbv below 10 km altitude with a similar seasonal cycle, though with a lower relative amplitude than for CO. Although same-day enhancements up to a factor of 1.87 for HCN and 1.24 for CO were measured relative to values predicted by a fit to the time series that accounts for the seasonal cycles and trends of both molecules, excluding time periods of elevated fire emissions has no significant impact on the best-fit long-term free tropospheric CO and HCN trends. Our result of no long-term CO trend since the late 1970s suggests that the global average long-term decline reported from 1990 through 1995 measurements has not continued in the free troposphere. Similarly, a fit to the full time series of 208 HCN free tropospheric daily averages with the same model yields an average 2.09–10 km mixing ratio of 0.219 ppbv and a long-term trend of ( - 0.12 ± 0.14 ) % yr - 1 , 1 sigma, relative to the mean since 1978, also indicating no significant long-term trend above the lower mid-latitude continental US Kitt Peak station. The results for both molecules suggest the site was not significantly impacted by summer boreal fires during the time span of the measurements that in some years cause widespread pollution above northern higher latitude sites.

Within the framework of the Network for Detection of Atmospheric Composition Change (NDACC), regular ground-based Fourier transform infrared (FTIR) measurements of many species are performed at several locations. Inversion schemes provide vertical profile information and characterization of the retrieved products which are therefore relevant for contributing to the validation of MIPAS profiles in the stratosphere and upper troposphere. We have focused on the species HNO3 and N2O at 5 NDACC-sites distributed in both hemispheres, i.e., Jungfraujoch (46.5° N) and Kiruna (68° N) for the northern hemisphere, and Wollongong (34° S), Lauder (45° S) and Arrival Heights (78° S) for the southern hemisphere. These ground-based data have been compared with MIPAS offline profiles (v4.61) for the year 2003, collocated within 1000 km around the stations, in the lower to middle stratosphere. To get around the spatial collocation problem, comparisons have also been made between the same ground-based FTIR data and the corresponding profiles resulting from the stratospheric 4D-VAR data assimilation system BASCOE constrained by MIPAS data. This paper discusses the results of the comparisons and the usefullness of using BASCOE profiles as proxies for MIPAS data. It shows good agreement between MIPAS and FTIR N2O partial columns: the biases are below 5% for all the stations and the standard deviations are below 7% for the three mid-latitude stations, and below 10% for the high latitude ones. The comparisons with BASCOE partial columns give standard deviations below 4% for the mid-latitude stations to less than 8% for the high latitude ones. After making some corrections to take into account the known bias due to the use of different spectroscopic parameters, the comparisons of HNO3 partial columns show biases below 3% and standard deviations below 15% for all the stations except Arrival Heights (bias of 5%, standard deviation of 21%). The results for this species, which has a larger spatial variability, highlight the necessity of defining appropriate collocation criteria and of accounting for the spread of the observed airmasses. BASCOE appears to have more deficiencies in producing proxies of MIPAS HNO3 profiles compared to N2O, but the obtained standard deviation of less than 10% between BASCOE and FTIR is reasonable. Similar results on profiles comparisons are also shown in the paper, in addition to partial column ones.

We report average tropospheric CH 4 volume mixing ratios retrieved from a 27 year time series of high spectral resolution infrared solar absorption measurements recorded between May 1977 and July 2004 at the US National Solar Observatory station on Kitt Peak ( 31 . 9 ∘ N , 111 . 6 ∘ W , 2.09 km altitude) and their comparison with surface in situ sampling measurements recorded between 1983 and 2004 at the Climate Monitoring and Diagnostics Laboratory (CMDL) station at Niwot Ridge, Colorado ( 40 . 0 ∘ N , 105 . 5 ∘ W , 3013 m altitude). The two measurement sets therefore overlap for the 1983–2004 time period. An average tropospheric volume mixing ratios of 1814 ± 48 ppbv ( 1 ppbv = 10 - 9 per unit volume) has been derived from the solar absorption time series with a best-fit increase rate trend equal to 8.26 ± 2.20 ppbv yr - 1 in 1983 decreasing to 1.94 ± 3.69 ppbv yr - 1 in 2003. The CMDL measurements also show a continuous long-term CH 4 volume mixing ratio rise, with subsequent slowing down. A mean ratio of the retrieved average tropospheric volume mixing ratio to the CMDL volume mixing ratio for the overlapping time period of 1.038 ± 0.034 indicates agreement between both data sets within the quantified experimental errors.

The average tropospheric volume mixing ratios of chlorofluorocarbon 12 (CCl2F2) have been retrieved from high-spectral resolution ground-based infrared solar-absorption spectra recorded from March 1982 to October 2003 with the McMath Fourier transform spectrometer at the US National Solar Observatory facility on Kitt Peak in southern Arizona (31.9°N, 111.6°W, 2.09 km altitude). The retrievals are based on fits to the unresolved ν 8 band Q-branches near 922 cm - 1 using the SFIT2 retrieval algorithm. The annual increase rate was equal to ( 16.88 ± 1.37 ) parts per trillion ( 10 - 12 ) by volume at the beginning of the time series, March 1982, or ( 4.77 ± 0.04 ) % , 1 sigma, declining progressively to ( 2.49 ± 1.24 ) parts per trillion, by volume at the end, October 2003, or ( 0.46 ± 0.24 ) % , 1 sigma. Average tropospheric mixing ratios from the solar spectra have been compared with average surface flask and in situ sampling measurements from the Climate Monitoring and Diagnostics Laboratory (CMDL) station at Niwot Ridge, CO, (USA) (40.0°N, 105.5°W, 3013 m altitude). The average ratio and standard deviation of the monthly means of the retrieved tropospheric mixing ratios relative to the CMDL surface mixing ratios is ( 1.01 ± 0.03 ) for the overlapping time period. Both datasets demonstrate the progressive impact of the Montreal protocol and its strengthening amendments on the trend of CCl2F2, though a tropospheric decrease has yet to be observed.

Fourier transform infrared spectrometry has been used to retrieve the total column abundances of SF 6 at three locations in the northern hemisphere, i.e., the Ny– Alesund site in Spitsbergen/Norway at 79 ∘ N , the Jungfraujoch observatory in Switzerland at 47 ∘ N and the Kitt Peak observatory in Arizona, USA, at 32 ∘ N . The total column results have been converted to average tropospheric mixing ratios. The mean increases in these mixing ratios have been found to be equal to 0.31 ± 0.08 pptv yr - 1 at Ny Alesund, 0.24 ± 0.01 pptv yr - 1 at the Jungfraujoch and 0.28 ± 0.09 pptv yr - 1 at Kitt Peak for the common period March 1993 to March 2002, in agreement with corresponding CMDL data ( 0.21 ± 0.0002 pptv yr - 1 ) at the surface. The limited accuracy of the Ny Alesund and Kitt Peak data results from strong tropospheric water vapour interferences at these lower altitude sites. Observations at all three locations show that SF 6 is still accumulating in the atmosphere. Extrapolations of linear and second-order fits to the Jungfraujoch data predict tropospheric mixing ratios of SF 6 , respectively equal to 16.4 ± 0.5 and 14.7 ± 0.6 in 2050, and 28.2 ± 0.9 and 22.2 ± 0.8 pptv in 2100, significantly lower than those reported in the literature so far.

Infrared solar spectra recorded with the Fourier transform spectrometer in the McMath solar telescope complex on Kitt Peak (31.9°N latitude, 111.6°W, 2.09 km altitude), southwest of Tucson, Arizona, have been analyzed to retrieve average SF6 tropospheric mixing ratios over a two-decade time span. The analysis is based primarily on spectral fits to absorption by the intense, unresolved ν3 band Q branch at 947.9 cm −1 . A best fit to measurements recorded with SF6 near typical background concentrations yields a SF6 increase in the average tropospheric mixing ratio from 1.13 pptv (10−12 per unit volume) in March 1982 to 3.77 pptv in March 2002. The long-term increase by a factor of 3.34 over the time span is consistent with the rapid growth of surface mixing ratios measured in situ at Northern Hemisphere remote stations, though the infrared measurements show a large scatter. Average tropospheric mixing ratio enhancements above background by 2–3 orders of magnitude have been identified in spectra recorded on 5 days between November 1988 and April 1997. These spectra were individually analyzed in an attempt to detect the strongest 8– 12 μm band of SF5CF3, a molecule recently identified with an atmospheric growth that has closely paralleled the rise in SF6 during the past three decades. Absorption by the strongest SF5CF3 band was predicted to be above the noise level in the Kitt Peak spectrum with the highest average mean tropospheric SF6 mixing ratio, assuming the reported atmospheric SF5CF3/SF6 ratio and a room temperature absorption cross sections reported for the SF5CF3 903-cm−1 band. An upper limit of 8×1015 molecules cm −2 for the SF5CF3 total column was estimated for this case. We hypothesize that the highly elevated SF6 levels above Kitt Peak resulted from a local release experiment rather than production via electrochemical fluoridation of intermediate products, the proposed source of atmospheric SF5CF3. The absence of the SF5CF3 feature in the spectra with elevated SF6 is consistent with the absence of SF5CF3 reported in a pure SF6 sample.

CO vertical profiles have been retrieved from so- lar absorption FTIR spectra recorded at the NDSC station of the Jungfraujoch (46.5 N, 8 E and 3580 m a.s.l.) for the pe- riod from January 1997 to May 2001. The characterisation of these profiles has been established by an information con- tent analysis and an estimation of the error budgets. A partial validation of the profiles has been performed through com- parisons with correlative measurements. The average vol- ume mixing ratios (vmr) in the 3 km layer above the station have been compared with coincident surface measurements. The agreement between monthly means from both measure- ment techniques is very good, with a correlation coefficient of 0.87, and no significant bias observed. The FTIR total columns have also been compared to CO partial columns above 3580 m a.s.l. derived from the MOPITT (Measure- ment Of Pollution In The Troposphere) instrument for the pe- riod March 2000 to May 2001. Relative to the FTIR columns, the MOPITT partial columns exhibit a positive bias of 8±8% for daytime and of 4±7% for nighttime measurements. ments provide accurate measurements of total columns of many atmospheric trace gases. Profile retrieval algorithms improve the quality of the total column measurements while providing information on the vertical distributions. We present a characterisation and a partial validation of the re- trieved ground-based FTIR profiles of CO at the Network for the Detection of Stratospheric Changes (NDSC) Inter- national Scientific Station of the Jungfraujoch (ISSJ) in the Swiss Alps. The characterisation includes an information content analysis and a determination of the error budgets. The validation is performed through comparisons between the FTIR retrieved "surface" (3.58-6.5 km) vmr and correl- ative surface in situ measurements. We also present com- parisons between CO columns and profiles from the FTIR retrievals with MOPITT partial columns.

Free tropospheric HCN columns have been derived from infrared solar spectra recorded with the National Solar Observatory Fourier transform spectrometer on Kitt Peak, Arizona (31.9°N latitude, 111.6°W longitude, 2.09 km altitude) between May 1978 and May 2000. The time series show up to a factor of 2.4 enhancement during the strong El Ninos of 1982–1983 and 1997–1998, the most intense since 1970. The observations provide confirmation that HCN is a sensitive tracer of biomass burning emissions transported to the free troposphere. No statistically significant long-term trend in the HCN-free tropospheric column has been detected over the 22-year measurement period. The results illustrate the importance of long-term spectroscopic measurements for quantifying climate and atmospheric chemistry-related atmospheric changes.

Time series of free tropospheric carbon monoxide (CO), ethane (C 2 H 6 ), and hydrogen cyanide (HCN) column abundances have been derived from observations at the International Scientific Station of the Jungfraujoch (ISSJ) at 3.58-km altitude in the Swiss Alps (latitude 46.55°N, 7.98°E longitude). The free troposphere was assumed to extend from 3.58 to 11 km altitude, and the related columns were derived for all three molecules from high spectral resolution infrared solar spectra recorded between January 1995 and October 1999. The three molecules show distinct seasonal cycles with maxima during winter for CO and C 2 H 6 , and during spring for HCN. These seasonal changes are superimposed on interannual variations. The tropospheric columns of all three molecules were elevated during 1998. Increases were most pronounced for HCN with enhanced values throughout the year, up to a factor of 2 in January 1998 when compared to averages of the other years. The increased tropospheric columns coincide with the period of widespread wildfires during the strong El Nino warm phase of 1997-1998. The emission enhancements above ISSJ are less pronounced, and they peaked after the increases measured above Mauna Loa (19.55°N, 155.6°W). Tropospheric trends for CO, C 2 H 6 , and HCN of (2.40 ± 0.49), (0.47 ± 0.64), and (7.00 ± 1.61)% yr 1 (1 sigma) were derived for January 1995 to October 1999. However, if 1998 measurements are excluded from the fit, CO and HCN trends that are not statistically significant, and a statistically significant decrease in the C 2 H 6 tropospheric column, are inferred. Comparisons of the infrared CO columns with CO in situ surface measurements suggest that the CO free tropospheric vertical volume mixing ratio profile generally decreases with altitude throughout the year.

Vertical profiles of infrared cirrus extinction have been derived from tropical and subtropical upper tropospheric solar occultation spectra. The measurements were recorded by the Atmospheric Trace Molecule Spectroscopy (ATMOS) Fourier transform spectrometer during the Atmospheric Laboratory for Applications and Sciences (ATLAS) 3 shuttle flight in November 1994. The presence of large numbers of small ice crystals is inferred from the appearance of broad extinction features in the 8-12 micron region. These features were observed near the tropopause and at lower altitudes. Vertical profiles of the ice extinction (/km) in microwindows at 831, 957, and 1204/cm have been retrieved from the spectra and analyzed with a model for randomly oriented spheroidal ice crystals. An area-equivalent spherical radius of 6 gm is estimated from the smallest ice crystals observed in the 8-12 micron region. Direct penetration of clouds into the lower stratosphere is inferred from observations of cloud extinction extending from the upper troposphere to 50 mbar (20 km altitude). Cloud extinction between 3 and 5 micron shows very little wavelength dependence, at least for the cases observed by the ATMOS instrument in the tropics and subtropics during ATLAS 3.

Time series of CO and C2H, measurements have been derived from high-resolution infrared solar spectra recorded in Lauder, New Zealand (45.0 degrees S, 169.7 degrees E, altitude 0.37 km), and at the U.S. National Solar Observatory (31.9 degrees N, 11, 1.6 degrees W, altitude 2.09 km) on Kitt Peak. Lauder observations were obtained between July 1993 and November 1997, while the Kitt Peak measurements were recorded between May 1977 and December 1997. Both databases were analyzed with spectroscopic parameters that included significant improvements for C2H6 relative to previous studies. Target CO and C2H6 lines were selected to achieve similar vertical samplings based on averaging kernels. These calculations show that partial columns from layers extending from the surface to the mean tropopause and from the mean tropopause to 100 km are nearly independent. Retrievals based on a semiempirical application of the Rodgers optimal estimation technique are reported for the lower layer, which has a broad maximum in sensitivity in the upper troposphere. The Lauder CO and C2H, partial columns exhibit highly asymmetrical seasonal cycles with minima in austral autumn and sharp peaks in austral spring. The spring maxima are the result of tropical biomass burning emissions followed by deep convective vertical transport to the upper troposphere and long-range horizontal transport. Significant year-to-year variations are observed for both CO and C2H6, but the measured trends, (+0.37 +/- 0.57)% yr(exp -1) and (-0.64 +/- 0.79)% yr(exp -1), I sigma, respectively, indicate no significant long-term changes. The Kitt Peak data also exhibit CO and C2H6, seasonal variations in the lower layer with trends equal to (-0.27 +/- 0.17)% yr(exp -1) and (-1.20 +/- 0.35)% yr(exp -1), 1 sigma, respectively. Hence a decrease in the Kitt Peak tropospheric C2H6 column has been detected, though the CO trend is not significant. Both measurement sets are compared with previous observations, reported trends, and three-dimensional model calculations.

Results of the comparison of carbon monoxide ground-based infrared solar spectroscopic measurements with data obtained during 1994 Measurement of Air Pollution From Space (MAPS) flights are presented. Spectroscopic measurements were performed correlatively with April and October MAPS flights by nine research groups from Belgium, Canada, Germany, Japan, New Zealand, Russia, and the United States. Characterization of the techniques and error analysis were performed. The role of the CO a priori profile used in the retrieval was estimated. In most cases an agreement between spectroscopic and MAPS data is within estimated MAPS accuracy of _+ 10%.

Since 1984, about 15000 high quality infrared solar spectra have beenrecorded with state-of-the-art grating and Fourier transform spectrometersat the International Scientific Station of the Jungfraujoch, Switzerland.Nonlinear least squares spectral curve fitting of selected microwindowscontaining isolated and well characterized lines of 20 telluric gases haveallowed to retrieve their total vertical column abundances above thestation, leading to observational data bases essential to derive long- andshort-term changes experienced by these species during the last 12 years. Inthis paper, we focus on atmospheric gases of particular interest within thecontext of the EUROTRAC/TOR (Tropospheric Ozone Research) project; secularevolution as well as seasonal cycles of the minor constituentsCH4, CO and of the trace gasesC2H6, OCS, C2H2, HCNand H2CO are reported and discussed. The long-livedN2O is included as a tracer of the dynamic activity of theatmosphere.

The goal of this study is to determine how H2O and HDO measurements in water vapor can be used to detect and diagnose biases in the representation of processes controlling tropospheric humidity in atmospheric general circulation models (GCMs). We analyze a large number of isotopic data sets (four satellite, sixteen ground-based remote-sensing, five surface in situ and three aircraft data sets) that are sensitive to different altitudes throughout the free troposphere. Despite significant differences between data sets, we identify some observed HDO/H2O characteristics that are robust across data sets and that can be used to evaluate models. We evaluate the isotopic GCM LMDZ, accounting for the effects of spatiotemporal sampling and instrument sensitivity. We find that LMDZ reproduces the spatial patterns in the lower and mid troposphere remarkably well. However, it underestimates the amplitude of seasonal variations in isotopic composition at all levels in the subtropics and in midlatitudes, and this bias is consistent across all data sets. LMDZ also underestimates the observed meridional isotopic gradient and the contrast between dry and convective tropical regions compared to satellite data sets. Comparison with six other isotope-enabled GCMs from the SWING2 project shows that biases exhibited by LMDZ are common to all models. The SWING2 GCMs show a very large spread in isotopic behavior that is not obviously related to that of humidity, suggesting water vapor isotopic measurements could be used to expose model shortcomings. In a companion paper, the isotopic differences between models are interpreted in terms of biases in the representation of processes controlling humidity. Copyright © 2012 by the American Geophysical Union.

Series of high-resolution infrared solar spectra recorded at the International Scientific Station of the Jungfraujoch, Switzerland, between 06/1986 and 11/1992, and at Kitt Peak National Observatory, Tucson, Arizona (U.S.A.), from 12/1980 to 04/1992, have been analyzed to provide a comprehensive ensemble of vertical column abundances of CHClF2 (HCFC-22; Freon-22) above the European and the North American continents. The columns were derived from nonlinear least-squares curve fittings between synthetic spectra and the observations containing the unresolved 2 nu(sub 6) Q-branch absorption of CHClF2 at 829.05/cm. The changes versus time observed in these columns were modeled assuming both an exponential and a linear increase with time. The exponential rates of increase at one-sigma uncertainties were found equal to (7.0 +/- 0.35)%/yr for the Junfraujoch data and (7.0 +/- 0.23)%/yr for the Kitt Peak data. The exponential trend of 7.0%/yr found at both stations widely separated in location can be considered as representative of the global increase of the CHClF2 burden in the Earth's atmosphere during the period 1980 to 1992. When assuming two realistic vertical volume mixing ratio profiles for CHClF2 in the troposphere, one quasi constant and the other decreasing by about 13% from the ground to the tropopause, the concentrations for mid-1990 were found to lie between 97 and 111 pptv (parts per trillion by volume) at the 3.58 km altitude of the Jungfraujoch and between 97 and 103 pptv at Kitt Peak, 2.09 km above sea level. Corresponding values derived from calculations using a high vertical resolution-2D model and recently compiled HCFC-22 releases to the atmosphere, were equal to 107 and 105 pptv, respectively, in excellent agreement with the measurements. The model calculated lifetime of CHClF2 was found equal to 15.6 years. The present results are compared critically with similar data found in the literature. On average, the concentrations found here are lower by 15-20% than those derived from in situ investigations; this difference cannot be explained by the absolute uncertainty of +/- 11% assigned presently to the infrared remote measurements.

Within the atmospheric research community, there is a strong interest in integrated datasets, combining data from several instrumentations. This integration is complicated by the different characteristics of the datasets, inherent to the measurement techniques. Here we have compared two carbon monoxide time series (1997 till 2007) acquired at the high-Alpine research station Jungfraujoch (3580 m above sea level), with two well-established measurement techniques, namely in situ surface concentration measurements using Non-Dispersive Infrared Absorption technology (NDIR), and ground-based remote sensing measurements using solar absorption Fourier Transform Infrared spectrometry (FTIR). The profile information available in the FTIR signal allowed us to extract an independent layer with a top height of 7.18 km above sea level, appropriate for comparison with our in situ measurements. We show that, even if both techniques are able to measure free troposphere CO concentrations, the datasets exhibit marked differences in their overall trends (−3.21 ± 0.03 ppb year−1 for NDIR vs. −0.8 ± 0.4 ppb year−1 for FTIR). Removing measurements that are polluted by uprising boundary layer air has a strong impact on the NDIR trend (now −2.62 ± 0.03 ppb year−1), but its difference with FTIR remains significant. Using the LAGRANTO trajectory model, we show that both measurement techniques are influenced by different source regions and therefore are likely subject to exhibit significant differences in their overall trend behaviour. However the observation that the NDIR-FTIR trend difference is as significant before as after 2001 is at odds with available emission databases which claim a significant Asian CO increase after 2001 only., Atmospheric Chemistry and Physics, 11 (13), ISSN:1680-7375, ISSN:1680-7367

This paper reports on daytime total vertical column abundances of formic acid (HCOOH) above the Northern mid-latitude, high altitude Jungfraujoch station (Switzerland; 46.5° N, 8.0° E, 3580 m alt.). The columns were derived from the analysis of infrared solar observations regularly performed with high spectral resolution Fourier transform spectrometers during over 1500 days between September 1985 and September 2007. The investigation was based on the spectrometric fitting of five spectral intervals, one encompassing the HCOOH ν6 band Q branch at 1105 cm-1, and four additional ones allowing to optimally account for critical temperature-sensitive or time-evolving interferences by other atmospheric gases, in particular HDO, CCl2F2 and CHClF2. The main results derived from the 22 years long database indicate that the free tropospheric burden of HCOOH above the Jungfraujoch undergoes important short-term daytime variability, diurnal and seasonal modulations, inter-annual anomalies, but no significant long-term background change. A major progress in the remote determination of the atmospheric HCOOH columns reported here has resulted from the adoption of new, improved absolute spectral line intensities for the infrared ν6 band of trans-formic acid, resulting in retrieved free tropospheric loadings being about a factor two smaller than if derived with previous spectroscopic parameters. Implications of this significant change with regard to earlier remote measurements of atmospheric formic acid and comparison with relevant Northern mid-latitude findings, both in situ and remote, will be assessed critically. Sparse HCOOH model predictions will also be evoked and assessed with respect to findings reported here. © 2010 Author(s)., SCOPUS: ar.j, info:eu-repo/semantics/published

Atmospheric CH3OH (methanol) free tropospheric (2.09-14-km altitude) time series spanning 22 years has been analyzed on the basis of high-spectral resolution infrared solar absorption spectra of the strong n8 band recorded from the U.S. National Solar Observatory on Kitt Peak (latitude 31.9degN, 111.6degW, 2.09-km altitude) with a 1-m Fourier transform spectrometer (FTS). The measurements span October 1981 to December 2003 and are the first long time series of CH3OH measurements obtained from the ground. The results were analyzed with SFIT2 version 3.93 and show a factor of three variations with season, a maximum at the beginning of July, a winter minimum, and no statistically significant long-term trend over the measurement time span.

Ground-based high spectral resolution Fourier-transform infrared (FTIR) solar absorption spectroscopy is a powerful remote sensing technique to obtain information on the total column abundances and on the vertical distribution of various constituents in the atmosphere. This work presents results from two FTIR measurement campaigns in 2002 and 2004, held at Ile de La Réunion (21° S, 55° E). These campaigns represent the first FTIR observations carried out at a southern (sub)tropical site. They serve the initiation of regular, long-term FTIR monitoring at this site in the near future. To demonstrate the capabilities of the FTIR measurements at this location for tropospheric and stratospheric monitoring, a detailed report is given on the retrieval strategy, information content and corresponding full error budget evaluation for ozone (O3), methane (CH4), nitrous oxide (N2O), carbon monoxide (CO), ethane (C2H6), hydrogen chloride (HCl), hydrogen fluoride (HF) and nitric acid (HNO3) total and partial column retrievals. Moreover, we have made a thorough comparison of the capabilities at sea level altitude (St.-Denis) and at 2200 m a.s.l. (Maïdo). It is proved that the performances of the technique are such that the atmospheric variability can be observed, at both locations and in distinct altitude layers. Comparisons with literature and with correlative data from ozone sonde and satellite (i.e., ACE-FTS, HALOE and MOPITT) measurements are given to confirm the results. Despite the short time series available at present, we have been able to detect the seasonal variation of CO in the biomass burning season, as well as the impact of particular biomass burning events in Africa and Madagascar on the atmospheric composition above Ile de La Réunion. We also show that differential measurements between St.-Denis and Maïdo provide useful information about the concentrations in the boundary layer.

[1] The first space-based measurements of upper tropospheric (110–300 hPa) formic acid (HCOOH) are reported from 0.02 cm−1 resolution Atmospheric Chemistry Experiment (ACE) Fourier transform spectrometer solar occultation measurements at 16°S–43°S latitude during late September to early October in 2004 and 2005. A maximum upper tropospheric HCOOH mixing ratio of 3.13 ± 0.02 ppbv (1 ppbv = 10−9 per unit volume), 1 sigma, at 10.5 km altitude was measured during 2004 at 29.97°S latitude and a lower maximum HCOOH mixing ratio of 2.03 ± 0.28 ppbv, at 9.5 km altitude was measured during 2005. Fire counts, back trajectories, and correlations of HCOOH mixing ratios with ACE simultaneous measurements of other fire products confirm the elevated HCOOH mixing ratios originated primarily from tropical fire emissions. A HCOOH emission factor relative to CO of 1.99 ± 1.34 g kg−1 during 2004 in upper tropospheric plumes is inferred from a comparison with lower mixing ratios measured during the same time period assuming HITRAN 2004 spectroscopic parameters.