Constraints for the photolysis rate and the equilibrium constant of ClO-dimer from airborne and balloon-borne measurements of chlorine compounds

We analyze measurements of ClO across the terminator taken by the Airborne Submillimeter Radiometer (ASUR) in the activated vortices of the Arctic winters of 1995/1996, 1996/1997, and 1999/2000 to evaluate the plausibility of various determinations of the ClO-dimer photolysis cross section and the rate constant controlling the thermal equilibrium between ClO-dimer and ClO. We use measured ClO during sunlit conditions to estimate total active chlorine (ClOx). As the measurements suggest nearly full chlorine activation in winter 1999/2000, we compare ClOx estimates based on various photolysis frequencies of ClO-dimer with total available inorganic chlorine (Cly), estimated from an N2O-Cly correlation established by a balloon-borne MkIV interferometer measurement. Only ClO-dimer cross sections leading to the fastest photolysis frequencies in the literature (including the latest evaluation by the Jet Propulsion Laboratory) give ClOx mixing ratios that overlap with the estimated range of available Cly. Slower photolysis rates lead to ClOx values that are higher than available Cly. We use the ClOx calculated from sunlit ClO measurements to estimate ClO in darkness based on different equilibrium constants, and compare it with ASUR ClO measurements before sunrise at high solar zenith angles. Calculations with equilibrium constants published in recent evaluations of the Jet Propulsion Laboratory give good agreement with observed ClO mixing ratios. Equilibrium constants leading to a higher ClO/ClOx ratio in darkness yield ClO values that tend to exceed observed abundances. Perturbing the rates for the ClO + BrO reaction in a manner that increases OClO formation and decreases BrCl formation leads to lower ClO values calculated for twilight conditions after sunset, resulting in better agreement with ASUR measurements

CH₄, CO, and H₂O spectroscopy for the sentinel-5 precursor mission: an assessment with the total carbon column observing network measurements

The TROPOspheric Monitoring Instrument (TROPOMI) will be part of ESA’s Sentinel-5 Precursor (S5P) satellite platform scheduled for launch in 2015. TROPOMI will monitor methane and carbon monoxide concentrations in the Earth’s atmosphere by measuring spectra of back-scattered sunlight in the short-wave infrared (SWIR). S5P will be the first satellite mission to rely uniquely on the spectral window at 4190–4340 cm−1 (2.3 μm) to retrieve CH4 and CO. In this study, we investigated if the absorption features of the three relevant molecules CH4, CO, and H2O are adequately known. To this end, we retrieved total columns of CH4, CO, and H2O from absorption spectra measured by two ground-based Fourier transform spectrometers that are part of the Total Carbon Column Observing Network (TCCON). The retrieval results from the 4190–4340 cm−1 range at the TROPOMI resolution (0.45 cm−1) were then compared to the CH4 results obtained from the 6000 cm−1 region, and the CO results obtained from the 4190–4340 cm−1 region at the higher TCCON resolution (0.02 cm−1). For TROPOMI-like settings, we were able to reproduce the CH4 columns to an accuracy of 0.3% apart from a constant bias of 1 %. The CO retrieval accuracy was, through interference, systematically influenced by the shortcomings of the CH4 and H2O spectroscopy. In contrast to CH4, the CO column error also varied significantly with atmospheric H2O content. Unaddressed, this would introduce seasonal and latitudinal biases to the CO columns retrieved from TROPOMI measurements. We therefore recommend further effort from the spectroscopic community to be directed at the H2O and CH4 spectroscopy in the 4190–4340 cm−1 region

Derivation of tropospheric methane from TCCON CH4and HF total column observations

The Total Carbon Column Observing Network (TCCON) is a global ground-based network of Fourier transform spectrometers that produce precise measurements of column-averaged dry-air mole fractions of atmospheric methane (CH4). Temporal variability in the total column of CH4 due to stratospheric dynamics obscures fluctuations and trends driven by tropospheric transport and local surface fluxes that are critical for understanding CH4 sources and sinks. We reduce the contribution of stratospheric variability from the total column average by subtracting an estimate of the stratospheric CH4 derived from simultaneous measurements of hydrogen fluoride (HF). HF provides a proxy for stratospheric CH4 because it is strongly correlated to CH4 in the stratosphere, has an accurately known tropospheric abundance (of zero), and is measured at most TCCON stations. The stratospheric partial column of CH4 is calculated as a function of the zonal and annual trends in the relationship between CH4 and HF in the stratosphere, which we determine from ACE-FTS satellite data. We also explicitly take into account the CH4 column averaging kernel to estimate the contribution of stratospheric CH4 to the total column. The resulting tropospheric CH4 columns are consistent with in situ aircraft measurements and augment existing observations in the troposphere

Comparison of XH₂O retrieved from GOSAT short-wavelength infrared spectra with observations from the TCCON network

Understanding the atmospheric distribution of water (H$_{2}$O) is crucial for global warming studies and climate change mitigation. In this context, reliable satellite data are extremely valuable for their global and continuous coverage, once their quality has been assessed. Short-wavelength infrared spectra are acquired by the Thermal And Near-infrared Sensor for carbon Observation-Fourier Transform Spectrometer (TANSO-FTS) aboard the Greenhouse gases Observing Satellite (GOSAT). From these, column-averaged dry-air mole fractions of carbon dioxide, methane and water vapor (XH$_{2}$O) have been retrieved at the National Institute for Environmental Studies (NIES, Japan) and are available as a Level 2 research product. We compare the NIES XH$_{2}$O data, Version 02.21, with retrievals from the ground-based Total Carbon Column Observing Network (TCCON, Version GGG2014). The datasets are in good overall agreement, with GOSAT data showing a slight global low bias of -3.1%± 17.7%, reasonable consistency over different locations (station bias of -3.1%±9.5%) and very good correlation with TCCON (R = 0.95). We identified two potential sources of discrepancy between the NIES and TCCON retrievals over land. While the TCCON XH$_{2}$O amounts can reach 6000–6500ppm when the atmospheric water content is high, the correlated NIES values do not exceed 5500 ppm. This could be due to a dry bias of TANSO-FTS in situations of high humidity and aerosol content. We also determined that the GOSAT-TCCON differences directly depend on the altitude difference between the TANSO-FTS footprint and the TCCON site. Further analysis will account for these biases, but the NIES V02.21 XH$_{2}$O product, after public release, can already be useful for water cycle studies

MIPAS IMK/IAA CFC-11 (CCl₃F) and CFC-12 (CCl₂F₂) measurements: Accuracy, precision and long-term stability

Profiles of CFC-11 (CCl$_{3}$F) and CFC-12 (CCl$_{2}$F$_{2}$) of the Michelson Interferometer for Passive Atmospheric Sounding (MIPAS) aboard the European satellite Envisat have been retrieved from versions MIPAS/4.61 to MIPAS/ 4.62 and MIPAS/5.02 to MIPAS/5.06 level-1b data using the scientific level-2 processor run by Karlsruhe Institute of Technology (KIT), Institute of Meteorology and Climate Research (IMK) and Consejo Superior de Investigaciones Científicas (CSIC), Instituto de Astrofísica de Andalucía (IAA). These profiles have been compared to measurements taken by the balloon-borne cryosampler, Mark IV (MkIV) and MIPAS-Balloon (MIPAS-B), the airborne MIPAS-STRatospheric aircraft (MIPAS-STR), the satellite-borne Atmospheric Chemistry Experiment Fourier transform spectrometer (ACE-FTS) and the High Resolution Dynamic Limb Sounder (HIRDLS), as well as the groundbased Halocarbon and other Atmospheric Trace Species (HATS) network for the reduced spectral resolution period (RR: January 2005–April 2012) of MIPAS. ACE-FTS, MkIV and HATS also provide measurements during the high spectral resolution period (full resolution, FR: July 2002–March 2004) and were used to validate MIPAS CFC-11 and CFC- 12 products during that time, as well as profiles from the Improved Limb Atmospheric Spectrometer, ILAS-II. In general, we find that MIPAS shows slightly higher values for CFC-11 at the lower end of the profiles (below 15 km) and in a comparison of HATS ground-based data and MIPAS measurements at 3 km below the tropopause. Differences range from approximately 10 to 50 pptv ( ~5–20 %) during the RR period. In general, differences are slightly smaller for the FR period. An indication of a slight high bias at the lower end of the profile exists for CFC-12 as well, but this bias is far less pronounced than for CFC-11 and is not as obvious in the relative differences between MIPAS and any of the comparison instruments. Differences at the lower end of the profile (below ~15 km) and in the comparison of HATS and MIPAS measurements taken at 3 km below the tropopause mainly stay within 10–50 pptv (corresponding to ~ 2–10% for CFC-12) for the RR and the FR period. Between ~15 and 30 km, most comparisons agree within 10–20 pptv (10–20 %), apart from ILAS-II, which shows large differences above ~17 km. Overall, relative differences are usually smaller for CFC-12 than for CFC-11. For both species – CFC-11 and CFC-12 – we find that differences at the lower end of the profile tend to be larger at higher latitudes than in tropical and subtropical regions. In addition, MIPAS profiles have a maximum in their mixing ratio around the tropopause, which is most obvious in tropical mean profiles. Comparisons of the standard deviation in a quiescent atmosphere (polar summer) show that only the CFC-12 FR error budget can fully explain the observed variability, while for the other products (CFC-11 FR and RR and CFC-12 RR) only two-thirds to three-quarters can be explained. Investigations regarding the temporal stability show very small negative drifts in MIPAS CFC-11 measurements. These instrument drifts vary between ~1 and 3% decade$^{-1}$. For CFC-12, the drifts are also negative and close to zero up to ~30 km. Above that altitude, larger drifts of up to 50% decade$^{-1}$ appear which are negative up to ~35 km and positive, but of a similar magnitude, above

Infra-red emission spectroscopy for atmospheric measurements from balloons

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An empirical study on the importance of a speed-dependent Voigt line shape model for tropospheric water vapor profile remote sensing

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Global carbon tetrachloride distributions obtained from the Atmospheric Chemistry Experiment (ACE)

The first study of the global atmospheric distribution of carbon tetrachloride (CC1), as a function of altitude and latitude, was performed using solar occultation measurements obtained by the Atmospheric Chemistry Experiment (ACE) mission using Fourier transform spectroscopy. A total of 8703 profile measurements were taken in the upper troposphere and lower stratosphere between February 2004 and August 2007. The zonal distribution of carbon tetrachloride displays a slight hemispheric asymmetry and decreasing concentration with increasing altitude at all latitudes. Maximum carbon tetrachloride concentrations are situated below 10 km in altitude with VMR (Volume Mixing Ratio) values of 100-130 ppt (parts per trillion). The highest concentrations are located about the Equator and at mid-latitudes, particularly for latitudes in heavily industrialised regions (2045° N), with values declining towards the poles. Global distributions obtained from ACE were compared with predictions from three chemistry transport models showing good agreement in terms of the vertical gradient despite an overall offset. The ACE dataset gives unique global and temporal coverage of carbon tetrachloride and its transport through the atmosphere. An estimated lifetime for carbon tetrachloride of 34±5 years was determined through correlation with CFC-11