Atmospheric Chemistry Experiment Research Articles

Sunset–sunrise difference in solar occultation ozone measurements (SAGE II, HALOE, and ACE–FTS) and its relationship to tidal vertical winds

Abstract. This paper contains a comprehensive investigation of the sunset–sunrise difference (SSD, i.e., the sunset-minus-sunrise value) of the ozone mixing ratio in the latitude range of 10° S–10° N. SSD values were determined from solar occultation measurements based on data obtained from the Stratospheric Aerosol and Gas Experiment (SAGE) II, the Halogen Occultation Experiment (HALOE), and the Atmospheric Chemistry Experiment–Fourier transform spectrometer (ACE–FTS). The SSD was negative at altitudes of 20–30 km (−0.1 ppmv at 25 km) and positive at 30–50 km (+0.2 ppmv at 40–45 km) for HALOE and ACE–FTS data. SAGE II data also showed a qualitatively similar result, although the SSD in the upper stratosphere was 2 times larger than those derived from the other data sets. On the basis of an analysis of data from the Superconducting Submillimeter-Wave Limb-Emission Sounder (SMILES) and a nudged chemical transport model (the specified dynamics version of the Whole Atmosphere Community Climate Model: SD–WACCM), we conclude that the SSD can be explained by diurnal variations in the ozone concentration, particularly those caused by vertical transport by the atmospheric tidal winds. All data sets showed significant seasonal variations in the SSD; the SSD in the upper stratosphere is greatest from December through February, while that in the lower stratosphere reaches a maximum twice: during the periods March–April and September–October. Based on an analysis of SD–WACCM results, we found that these seasonal variations follow those associated with the tidal vertical winds.

Comparison of upper tropospheric carbon monoxide from MOPITT, ACE‐FTS, and HIPPO‐QCLS

AbstractProducts from the Measurements Of Pollution In The Troposphere (MOPITT) instrument are regularly validated using in situ airborne measurements. However, few of these measurements reach into the upper troposphere, thus hindering MOPITT validation in that region. Here we evaluate upper tropospheric (~500 hPa to the tropopause) MOPITT CO profiles by comparing them to satellite Atmospheric Chemistry Experiment Fourier Transform Spectrometer (ACE‐FTS) retrievals and to measurements from the High‐performance Instrumented Airborne Platform for Environmental Research Pole to Pole Observations (HIPPO) Quantum Cascade Laser Spectrometer (QCLS). Direct comparison of colocated v5 MOPITT thermal infrared‐only retrievals, v3.0 ACE‐FTS retrievals, and HIPPO‐QCLS measurements shows a slight positive MOPITT CO bias within its 10% accuracy requirement with respect to the other two data sets. Direct comparison of colocated ACE‐FTS and HIPPO‐QCLS measurements results in a small number of samples due to the large disparity in sampling pattern and density of these data sets. Thus, two additional indirect techniques for comparison of noncoincident data sets have been applied: tracer‐tracer (CO‐O3) correlation analysis and analysis of profiles in tropopause coordinates. These techniques suggest a negative bias of ACE‐FTS with respect to HIPPO‐QCLS; this could be caused by differences in resolution (horizontal, vertical) or by deficiencies in the ACE‐FTS CO retrievals below ~20 km of altitude, among others. We also investigate the temporal stability of MOPITT and ACE‐FTS data, which provide unique global CO records and are thus important in climate analysis. Our results indicate that the relative bias between the two data sets has remained generally stable during the 2004–2010 period.

Derived methane in the stratosphere and lower mesosphere from Aura Microwave Limb Sounder measurements of nitrous oxide, water vapor, and carbon monoxide

The global distribution of methane (CH4) in the stratosphere and lower mesosphere has been derived using coincident measurements of water vapor (H2O), carbon monoxide (CO), and nitrous oxide (N2O) from the Microwave Limb Sounder (MLS) instrument on the Aura satellite. The derivation method is based on empirical relationships between these species established using observations from the Atmospheric Chemistry Experiment—Fourier Transform Spectrometer (ACE-FTS) on the SCISAT I satellite. The observed correlation between CH4 and N2O from ACE-FTS is used to derive CH4 from MLS measurements of N2O in the lower stratosphere, extending from a pressure of 100 hPa to a range of 30–10 hPa, depending on atmospheric conditions. In the upper stratosphere and lower mesosphere, between 30–10 hPa and 0.1 hPa, correlations between CH4 and H2O are used to derive CH4 from MLS measurements of H2O. Coincident MLS measurements of CO are utilized to separate two distinct air mass regimes in the CH4 - H2O relationship. This new methane data set covers all seasons and latitudes observed by MLS over the course of the Aura mission from 2004 to 2014. Examples are shown demonstrating the consistency of MLS derived CH4 with other trace gas measurements.

Satellite observations of stratospheric carbonyl fluoride

Abstract. The vast majority of emissions of fluorine-containing molecules are anthropogenic in nature, e.g. chlorofluorocarbons (CFCs), hydrochlorofluorocarbons (HCFCs), and hydrofluorocarbons (HFCs). These molecules slowly degrade in the atmosphere, leading to the formation of HF, COF2, and COClF, which are the main fluorine-containing species in the stratosphere. Ultimately both COF2 and COClF further degrade to form HF, an almost permanent reservoir of stratospheric fluorine due to its extreme stability. Carbonyl fluoride (COF2) is the second-most abundant stratospheric "inorganic" fluorine reservoir, with main sources being the atmospheric degradation of CFC-12 (CCl2F2), HCFC-22 (CHF2Cl), and CFC-113 (CF2ClCFCl2). This work reports the first global distributions of carbonyl fluoride in the Earth's atmosphere using infrared satellite remote-sensing measurements by the Atmospheric Chemistry Experiment Fourier transform spectrometer (ACE-FTS), which has been recording atmospheric spectra since 2004, and the Michelson Interferometer for Passive Atmospheric Sounding (MIPAS) instrument, which recorded thermal emission atmospheric spectra between 2002 and 2012. The observations reveal a high degree of seasonal and latitudinal variability over the course of a year. These have been compared with the output of SLIMCAT, a state-of-the-art three-dimensional chemical transport model. In general the observations agree well with each other, although MIPAS is biased high by as much as ~30%, and compare well with SLIMCAT. Between January 2004 and September 2010 COF2 grew most rapidly at altitudes above ~25 km in the southern latitudes and at altitudes below ~25 km in the northern latitudes, whereas it declined most rapidly in the tropics. These variations are attributed to changes in stratospheric dynamics over the observation period. The overall COF2 global trend over this period is calculated as 0.85 ± 0.34 (MIPAS), 0.30 ± 0.44 (ACE), and 0.88% year−1 (SLIMCAT).

Tropospheric nitric acid columns from the IASI satellite instrument interpreted with a chemical transport model: Implications for parameterizations of nitric oxide production by lightning

AbstractThis paper interprets tropical tropospheric nitric acid columns from the Infrared Atmospheric Sounding Interferometer (IASI) satellite instrument with a global chemical transport model (GEOS‐Chem). GEOS‐Chem and IASI columns generally agree over the tropical ocean to within 10%. However, the GEOS‐Chem simulation underestimates IASI nitric acid over Southeast Asia by a factor of 2. The regional nitric acid bias is confirmed by comparing the GEOS‐Chem simulation with additional satellite (High Resolution Dynamics Limb Sounder, Atmospheric Chemistry Experiment Fourier Transform Spectrometer) and aircraft (Pacific Exploratory Mission (PEM)‐Tropics A and PEM‐West B) observations of the middle and upper troposphere. This bias appears to be driven by the lightning NOx parameterization, both in terms of the magnitude of the NOx source and the ozone production efficiency of concentrated lightning NOx plumes. We tested a subgrid lightning plume parameterization and found that an ozone production efficiency of 15 mol/mol in lightning plumes over Southeast Asia in conjunction with an additional 0.5 Tg N would reduce the regional nitric acid bias from 92% to 6% without perturbing the rest of the tropics. Other sensitivity studies such as modified NOx yield per flash, increased altitude of lightning NOx emissions, decreased convective mass flux, or increased scavenging of nitric acid required unrealistic changes to reduce the bias.

Intercomparison of satellite and ground-based measurements of ozone, NO2, HF, and HCl near Saint Petersburg, Russia

Regular intercomparison of different observing systems is a part of their testing and validation protocol, which gives the estimates of real measurement errors. The main objective of our study is the comparison of satellite and ground-based measurements of atmospheric composition near Saint Petersburg, Russia. Since early 2009, high-resolution Fourier Transform Infrared (FTIR) solar absorption spectra have been recorded at Peterhof station (59.82° N, 29.88° E), located in the suburbs of Saint Petersburg. We derived column amounts of O3, HCl, HF, and NO2 from these spectra using the retrieval codes SFIT2 and PROFFIT. We compared the data retrieved from Bruker 125 HR FTIR measurements with coincident satellite observations of the Microwave Limb Sounding (MLS), Ozone Monitoring Instrument (OMI), Fourier Transform Spectrometer from Atmospheric Chemistry Experiment (ACE-FTS), Global Ozone Monitoring Experiment (GOME and GOME-2), and Scanning Imaging Absorption Spectrometer for Atmospheric Chartography (SCIAMACHY) instruments. The relative differences in ozone columns of FTIR from OMI-TOMS amount within (+3.4 ± 2.9)%, from GOME-2 are (+2.2 ± 3.0)%. The comparison of FTIR and MLS measurements of stratospheric ozone columns gives no mean and 5% of the RMS differences. Measurements of NO2 columns agree with the mean difference of +9% and the RMS differences within 14–16% for FTIR vs. GOME-2, SCIAMACHY, and OMI. FTIR vs. GOME comparison gives (+6 ± 31)%. HCl columns comparison for FTIR vs. MLS shows −4.5% in the mean and 12% in the RMS differences. FTIR vs. ACE-FTS comparison (nine cases) gives −8% and 10% for the mean and the RMS relative differences, respectively. Comparison of HF columns shows (−12 ± 6)% and (−12 ± 11)% for FTIR vs. ACE data v.2.2 and v.3.0, respectively. These figures show that the Peterhof ground-based FTIR measuring system can be used to support the validation of satellite data in the monitoring of stratospheric gases.

Retrieval of carbon dioxide vertical profiles from solar occultation observations and associated error budgets for ACE-FTS and CASS-FTS

Abstract. An algorithm is developed to retrieve the vertical profile of carbon dioxide in the 5 to 25 km altitude range using mid-infrared solar occultation spectra from the main instrument of the ACE (Atmospheric Chemistry Experiment) mission, namely the Fourier transform spectrometer (FTS). The main challenge is to find an atmospheric phenomenon which can be used for accurate tangent height determination in the lower atmosphere, where the tangent heights (THs) calculated from geometric and timing information are not of sufficient accuracy. Error budgets for the retrieval of CO2 from ACE-FTS and the FTS on a potential follow-on mission named CASS (Chemical and Aerosol Sounding Satellite) are calculated and contrasted. Retrieved THs have typical biases of 60 m relative to those retrieved using the ACE version 3.x software after revisiting the temperature dependence of the N2 CIA (collision-induced absorption) laboratory measurements and accounting for sulfate aerosol extinction. After correcting for the known residual high bias of ACE version 3.x THs expected from CO2 spectroscopic/isotopic inconsistencies, the remaining bias for tangent heights determined with the N2 CIA is −20 m. CO2 in the 5–13 km range in the 2009–2011 time frame is validated against aircraft measurements from CARIBIC (Civil Aircraft for the Regular Investigation of the atmosphere Based on an Instrument Container), CONTRAIL (Comprehensive Observation Network for Trace gases by Airline), and HIPPO (HIAPER Pole-to-Pole Observations), yielding typical biases of −1.7 ppm in the 5–13 km range. The standard error of these biases in this vertical range is 0.4 ppm. The multi-year ACE-FTS data set is valuable in determining the seasonal variation of the latitudinal gradient which arises from the strong seasonal cycle in the Northern Hemisphere troposphere. The annual growth of CO2 in this time frame is determined to be 2.6 ± 0.4 ppm year−1, in agreement with the currently accepted global growth rate based on ground-based measurements.

Trajectory model simulations of ozone (O<sub>3</sub>) and carbon monoxide (CO) in the lower stratosphere

Abstract. A domain-filling, forward trajectory model originally developed for simulating stratospheric water vapor is used to simulate ozone (O3) and carbon monoxide (CO) in the lower stratosphere. Trajectories are initialized in the upper troposphere, and the circulation is based on reanalysis wind fields. In addition, chemical production and loss rates along trajectories are included using calculations from the Whole Atmosphere Community Climate Model (WACCM). The trajectory model results show good overall agreement with satellite observations from the Aura Microwave Limb Sounder (MLS) and the Atmospheric Chemistry Experiment Fourier Transform Spectrometer (ACE-FTS) in terms of spatial structure and seasonal variability. The trajectory model results also agree well with the Eulerian WACCM simulations. Analysis of the simulated tracers shows that seasonal variations in tropical upwelling exerts strong influence on O3 and CO in the tropical lower stratosphere, and the coupled seasonal cycles provide a useful test of the transport simulations. Interannual variations in the tracers are also closely coupled to changes in upwelling, and the trajectory model can accurately capture and explain observed changes during 2005–2011. This demonstrates the importance of variability in tropical upwelling in forcing chemical changes in the tropical lower stratosphere.

ACE infrared spectral atlases of the Earth׳s atmosphere

Five infrared atmospheric atlases are presented using solar occultation spectra from the Atmospheric Chemistry Experiment Fourier Transform Spectrometer (ACE-FTS) in low earth orbit. The spectral atlases were created for Arctic summer, Arctic winter, mid-latitude summer, mid-latitude winter and the tropics. Each covers the spectral range from 700 to 4400cm−1 and consists of 31 spectra that span an altitude range of 6–126km in 4-km altitude intervals. To improve the signal-to-noise ratio, each spectrum in the atlas is an average of at least several hundred individual ACE-FTS limb transmission spectra. Representative plots in pdf format at 10km (troposphere), 30km (stratosphere), 70km (mesosphere), and 110km (lower thermosphere) are also available.

Five years of CO, HCN, C<sub>2</sub>H<sub>6</sub>, C<sub>2</sub>H<sub>2</sub>, CH<sub>3</sub>OH, HCOOH and H<sub>2</sub>CO total columns measured in the Canadian high Arctic

Abstract. We present a five-year time series of seven tropospheric species measured using a ground-based Fourier transform infrared (FTIR) spectrometer at the Polar Environment Atmospheric Research Laboratory (PEARL; Eureka, Nunavut, Canada; 80°05' N, 86°42' W) from 2007 to 2011. Total columns and temporal variabilities of carbon monoxide (CO), hydrogen cyanide (HCN) and ethane (C2H6) as well as the first derived total columns at Eureka of acetylene (C2H2), methanol (CH3OH), formic acid (HCOOH) and formaldehyde (H2CO) are investigated, providing a new data set in the sparsely sampled high latitudes. Total columns are obtained using the SFIT2 retrieval algorithm based on the optimal estimation method. The microwindows as well as the a priori profiles and variabilities are selected to optimize the information content of the retrievals, and error analyses are performed for all seven species. Our retrievals show good sensitivities in the troposphere. The seasonal amplitudes of the time series, ranging from 34 to 104%, are captured while using a single a priori profile for each species. The time series of the CO, C2H6 and C2H2 total columns at PEARL exhibit strong seasonal cycles with maxima in winter and minima in summer, in opposite phase to the HCN, CH3OH, HCOOH and H2CO time series. These cycles result from the relative contributions of the photochemistry, oxidation and transport as well as biogenic and biomass burning emissions. Comparisons of the FTIR partial columns with coincident satellite measurements by the Atmospheric Chemistry Experiment Fourier Transform Spectrometer (ACE-FTS) show good agreement. The correlation coefficients and the slopes range from 0.56 to 0.97 and 0.50 to 3.35, respectively, for the seven target species. Our new data set is compared to previous measurements found in the literature to assess atmospheric budgets of these tropospheric species in the high Arctic. The CO and C2H6concentrations are consistent with negative trends observed over the Northern Hemisphere, attributed to fossil fuel emission decrease. The importance of poleward transport for the atmospheric budgets of HCN and C2H2 is highlighted. Columns and variabilities of CH3OH and HCOOH at PEARL are comparable to previous measurements performed at other remote sites. However, the small columns of H2CO in early May might reflect its large atmospheric variability and/or the effect of the updated spectroscopic parameters used in our retrievals. Overall, emissions from biomass burning contribute to the day-to-day variabilities of the seven tropospheric species observed at Eureka.

Stratospheric warming influence on the mesosphere/lower thermosphere as seen by the extended CMAM

Abstract. The response of the upper mesosphere/lower thermosphere region to major sudden stratospheric warming (SSW) is examined employing temperature, winds, NOX and CO constituents from the extended Canadian Middle Atmosphere Model (CMAM) with continuous incremental nudging below 10 hPa (~ 30 km). The model results considered cover high latitudes (60–85° N) from 10 to 150 km height for the December–March period of 2003/2004, 2005/2006 and 2008/2009, when some of the strongest SSWs in recent years were observed. NOX and CO are used as proxies for examining transport. Comparisons with ACE-FTS (Atmospheric Chemistry Experiment–Fourier Transform Spectrometer) satellite observations show that the model represents well the dynamics of the upper mesosphere/lower thermosphere region, the coupling of the stratosphere–mesosphere, and the NOX and CO transport. New information is obtained on the upper mesosphere/lower thermosphere up to 150 km showing that the NOX volume mixing ratio in the 2003/2004 winter was very perturbed indicating transport from the lower atmosphere and intense mixing with large NOX influx from the thermosphere compared to 2006 and 2009. These results, together with those from other models and observations, clearly show the impact of stratospheric warmings on the thermosphere.

On the distribution of CO2 and CO in the mesosphere and lower thermosphere

AbstractWe have used the Whole Atmosphere Community Climate Model (WACCM) to calculate the distribution of CO2 and CO in the mesosphere and lower thermosphere (MLT), and we have compared the results with observations, mainly from the Atmospheric Chemistry Experiment Fourier Transform Spectrometer and Michelson Interferometer for Passive Atmospheric Sounding satellite‐borne instruments. We find that WACCM can reproduce the observed distribution of CO2 in the MLT and the rapid falloff of CO2 above about 80 km. Analysis of the principal terms in the calculated budget of CO2 shows that its global‐mean vertical profile is determined mainly by the competition between molecular diffusive separation and eddy mixing by gravity waves. The model underestimates somewhat the mixing ratio of CO2 in the thermosphere compared to that in the observations, but we show that the discrepancy may be eliminated by a reasonable adjustment of the Prandtl number used to calculate the diffusivity due to gravity waves. Simulated CO is also consistent with observations, except that in the standard version of the model, its mixing ratio is uniformly lower than observed above about 100 km. We conclude that WACCM likely underestimates the rate of production of CO in the lower thermosphere from photolysis of CO2 at wavelengths < 121 nm, and we show that this stems from the use of a very large absorption cross section for O2 in the wavelength range 105–121 nm. When a smaller cross section is used, photolysis of CO2 increases by a factor of 2–3 at ~ 95–115 km and, as a result, CO mixing ratios become larger and agree much more closely with observations. We emphasize that the increase in CO2 photolysis implies only minor changes in the vertical profile of CO2 because photolytic loss is a minor term in the budget of CO2 in the MLT.

Ethanol fuels ozone pollution

Shifts in use between petrol and ethanol in Sao Paulo’s cars creates unique atmospheric chemistry experiment.

Drift-corrected trends and periodic variations in MIPAS IMK/IAA ozone measurements

Abstract. Drifts, trends and periodic variations were calculated from monthly zonally averaged ozone profiles. The ozone profiles were derived from level-1b data of the Michelson Interferometer for Passive Atmospheric Sounding (MIPAS) by means of the scientific level-2 processor run by the Karlsruhe Institute of Technology (KIT), Institute for Meteorology and Climate Research (IMK). All trend and drift analyses were performed using a multilinear parametric trend model which includes a linear term, several harmonics with period lengths from 3 to 24 months and the quasi-biennial oscillation (QBO). Drifts at 2-sigma significance level were mainly negative for ozone relative to Aura MLS and Odin OSIRIS and negative or near zero for most of the comparisons to lidar measurements. Lidar stations used here include those at Hohenpeissenberg (47.8° N, 11.0° E), Lauder (45.0° S, 169.7° E), Mauna Loa (19.5° N, 155.6° W), Observatoire Haute Provence (43.9° N, 5.7° E) and Table Mountain (34.4° N, 117.7° W). Drifts against the Atmospheric Chemistry Experiment Fourier Transform Spectrometer (ACE-FTS) were found to be mostly insignificant. The assessed MIPAS ozone trends cover the time period of July 2002 to April 2012 and range from −0.56 ppmv decade−1 to +0.48 ppmv decade−1 (−0.52 ppmv decade−1 to +0.47 ppmv decade−1 when displayed on pressure coordinates) depending on altitude/pressure and latitude. From the empirical drift analyses we conclude that the real ozone trends might be slightly more positive/less negative than those calculated from the MIPAS data, by conceding the possibility of MIPAS having a very small (approximately within −0.3 ppmv decade−1) negative drift for ozone. This leads to drift-corrected trends of −0.41 ppmv decade−1 to +0.55 ppmv decade−1 (−0.38 ppmv decade−1 to +0.53 ppmv decade−1 when displayed on pressure coordinates) for the time period covered by MIPAS Envisat measurements, with very few negative and large areas of positive trends at mid-latitudes for both hemispheres around and above 30 km (~10 hPa). Negative trends are found in the tropics around 25 and 35 km (~25 and 5 hPa), while an area of positive trends is located right above the tropical tropopause. These findings are in good agreement with the recent literature. Differences of the trends compared with the recent literature could be explained by a possible shift of the subtropical mixing barriers. Results for the altitude–latitude distribution of amplitudes of the quasi-biennial, annual and the semi-annual oscillation are overall in very good agreement with recent findings.

ACE-FTS version 3.0 data set: validation and data processing update

On 12 August 2003, the Canadian-led Atmospheric Chemistry Experiment (ACE) was launched into a 74° inclination orbit at 650 km with the mission objective to measure atmospheric composition using infrared and UV-visible spectroscopy (Bernath et al. 2005). The ACE mission consists of two main instruments, ACE-FTS and MAESTRO (McElroy et al. 2007), which are being used to investigate the chemistry and dynamics of the Earth’s atmosphere. Here, we focus on the high resolution (0.02 cm-1) infrared Fourier Transform Spectrometer, ACE-FTS, that measures in the 750-4400 cm-1 (2.2 to 13.3 µm) spectral region. This instrument has been making regular solar occultation observations for more than nine years. The current ACE-FTS data version (version 3.0) provides profiles of temperature and volume mixing ratios (VMRs) of more than 30 atmospheric trace gas species, as well as 20 subsidiary isotopologues of the most abundant trace atmospheric constituents over a latitude range of ~85°N to ~85°S. This letter describes the current data version and recent validation comparisons and provides a description of our planned updates for the ACE-FTS data set. [...]

Middle atmospheric changes caused by the January and March 2012 solar proton events

Abstract. The recent 23–30 January and 7–11 March 2012 solar proton event (SPE) periods were substantial and caused significant impacts on the middle atmosphere. These were the two largest SPE periods of solar cycle 24 so far. The highly energetic solar protons produced considerable ionization of the neutral atmosphere as well as HOx (H, OH, HO2) and NOx (N, NO, NO2). We compute a NOx production of 1.9 and 2.1 Gigamoles due to these SPE periods in January and March 2012, respectively, which places these SPE periods among the 12 largest in the past 50 yr. Aura Microwave Limb Sounder (MLS) observations of the peroxy radical, HO2, show significant enhancements of > 0.9 ppbv in the northern polar mesosphere as a result of these SPE periods. Both MLS measurements and Goddard Space Flight Center (GSFC) two-dimensional (2-D) model predictions indicated middle mesospheric ozone decreases of > 20% for several days in the northern polar region with maximum depletions > 60% over 1–2 days as a result of the HOx produced in both the January and March 2012 SPE periods. The SCISAT-1 Atmospheric Chemistry Experiment Fourier Transform Spectrometer (ACE) and the Envisat Michelson Interferometer for Passive Atmospheric Sounding (MIPAS) instruments measured NO and NO2 (~ NOx), which indicated enhancements of over 20 ppbv in most of the northern polar mesosphere for several days as a result of these SPE periods. The GSFC 2-D model and the Global Modeling Initiative three-dimensional chemistry and transport model were used to predict the medium-term (~ months) influence and showed that the polar middle atmospheric ozone was most affected by these solar events in the Southern Hemisphere due to the increased downward motion in the fall and early winter. The downward transport moved the SPE-produced NOy to lower altitudes and led to predicted modest destruction of ozone (5–13%) in the upper stratosphere days to weeks after the March 2012 event. Polar total ozone reductions were predicted to be a maximum of 1.5% in 2012 due to these SPEs.

Carbonyl Sulphide (OCS) Variability with Latitude in the Atmosphere

Carbonyl sulphide (OCS) is an important precursor of sulphate aerosols and consequently a key species in stratospheric ozone depletion. The SPectromètre InfraRouge d'Absorption à Lasers Embarqués (SPIRALE) and shortwave infrared (SWIR) balloon-borne instruments have flown in the tropics and in the polar Arctic, and ground-based measurements have been performed by the Qualité de l'Air (QualAir) Fourier Transform Spectrometer in Paris. Partial and total columns and vertical profiles have been obtained to study OCS variability with altitude, latitude, and season. The annual total column variation in Paris reveals a seasonal variation with a maximum in April–June and a minimum in November–January. Total column measurements above Paris and from SWIR balloon-borne instrument are compared with several MkIV measurements, several Network for the Detection of Atmospheric Composition Change (NDACC) stations, aircraft, ship, and balloon measurements to highlight the OCS total column decrease from tropical to polar latitudes. OCS high-resolution in situ vertical profiles have been measured for the first time in the altitude range between 14 and 30 km at tropical and polar latitudes. OCS profiles are compared with Atmospheric Chemistry Experiment (ACE) satellite measurements and show good agreement. Using the correlation between OCS and N2O from SPIRALE, the OCS stratospheric lifetime has been accurately determined. We find a stratospheric lifetime of 68 ± 20 years at polar latitudes and 58 ± 14 years at tropical latitudes leading to a global stratospheric sink of 49 ± 14 Gg S y−1.

HCl and ClO profiles inside the Antarctic vortex as observed by SMILES in November 2009: comparisons with MLS and ACE-FTS instruments

Abstract. We present vertical profiles of hydrogen chloride (HCl) and chlorine monoxide (ClO) as observed by the Superconducting Submillimeter-Wave Limb-Emission Sounder (SMILES) on the International Space Station (ISS) inside the Antarctic vortex on 19–24 November 2009. The SMILES HCl value reveals 2.8–3.1 ppbv between 450 K and 500 K levels in potential temperature (PT). The high value of HCl is highlighted since it is suggested that HCl is a main component of the total inorganic chlorine (Cly), defined as Cly ≃ HCl + ClO + chlorine nitrate (ClONO2), inside the Antarctic vortex in spring, owing to low ozone values. To confirm the quality of two SMILES level 2 (L2) data products provided by the Japan Aerospace Exploration Agency (JAXA) and Japan's National Institute of Information and Communications Technology (NICT), vis-à-vis the partitioning of Cly, comparisons are made using other satellite data from the Aura Microwave Limb Sounder (MLS) and Atmospheric Chemistry Experiment Fourier Transform Spectrometer (ACE-FTS). HCl values from the SMILES NICT L2 product agree to within 10% (0.3 ppbv) with the MLS HCl data between 450 and 575 K levels in PT and with the ACE-FTS HCl data between 425 and 575 K. The SMILES JAXA L2 product is 10 to 20% (0.2–0.5 ppbv) lower than that from MLS between 400 and 700 K and from ACE-FTS between 500 and 700 K. For ClO in daytime, the difference between SMILES (JAXA and NICT) and MLS is less than ±0.05 ppbv (100 %) between 500 K and 650 K with the ClO values less than 0.2 ppbv. ClONO2 values as measured by ACE-FTS also reveal 0.2 ppbv at 475–500 K level, resulting in the HCl / Cly ratios of 0.91–0.95. The HCl / Cly ratios derived from each retrieval agree to within −5 to 8 % with regard to their averages. The high HCl values and HCl / Cly ratios observed by the three instruments in the lower stratospheric Antarctic vortex are consistent with previous observations in late Austral spring.

Variations in middle atmospheric water vapor from 2004 to 2013

AbstractWe show measurements of middle atmospheric water vapor as measured by two ground‐based Water Vapor Millimeter‐wave Spectrometer instruments and three satellite‐based instruments: the Aura Microwave Limb Sounder, the Atmospheric Chemistry Experiment (ACE), and the Michelson Interferometer for Passive Atmospheric Sounding (MIPAS). We also show CH4 measurements from the MIPAS and ACE instruments and use these to help interpret the H2O variations. We find that interannual changes in stratospheric H2O of ~0.5 ppmv, observed from Table Mountain, California, at 26 km and 40 km from 2010 to 2012, are caused primarily by dynamically driven changes in CH4 during this period. The interannual variations in H2O observed over Mauna Loa, Hawaii, are shown to be quite similar to the average variations observed over 50°S–50°N in the lower mesosphere; thus, we conclude that a single ground‐based microwave instrument can provide a useful estimate of interannual globally averaged lower mesospheric H2O variations, even when such changes are as small as ~0.2–0.3 ppmv. We find that the increase of ~0.2–0.3 ppmv in H2O in the lower mesosphere since 2006 is qualitatively consistent with an increase in tropical tropopause temperature since around 2001.

Diurnal variation of stratospheric and lower mesospheric HOCl, ClO and HO<sub>2</sub> at the equator: comparison of 1-D model calculations with measurements by satellite instruments

Abstract. The diurnal variation of HOCl and the related species ClO, HO2 and HCl measured by satellites has been compared with the results of a one-dimensional photochemical model. The study compares the data from various limb-viewing instruments with model simulations from the middle stratosphere to the lower mesosphere. Data from three sub-millimetre instruments and two infrared spectrometers are used, namely from the Sub-Millimetre Radiometer (SMR) on board Odin, the Microwave Limb Sounder (MLS) on board Aura, the Superconducting Submillimeter-wave Limb-Emission Sounder (SMILES) on the International Space Station, the Michelson Interferometer for Passive Atmospheric Sounding (MIPAS) on board ENVISAT, and the Atmospheric Chemistry Experiment Fourier Transform Spectrometer (ACE-FTS) on board SCISAT. Inter-comparison of the measurements from instruments on sun-synchronous satellites (SMR, MLS, MIPAS) and measurements from solar occultation instruments (ACE-FTS) is challenging since the measurements correspond to different solar zenith angles (or local times). However, using a model which covers all solar zenith angles and data from the SMILES instrument which measured at all local times over a period of several months provides the possibility to verify the model and to indirectly compare the diurnally variable species. The satellite data were averaged for latitudes of 20° S to 20° N for the SMILES observation period from November 2009 to April 2010 and were compared at three altitudes: 35, 45 and 55 km. Besides presenting the SMILES data, the study also shows a first comparison of the latest MLS data (version 3.3) of HOCl, ClO, and HO2 with other satellite observations, as well as a first evaluation of HO2 observations made by Odin/SMR. The MISU-1D model has been carefully initialised and run for conditions and locations of the observations. The diurnal cycle features for the species investigated here are generally well reproduced by the model. The satellite observations and the model agree well in terms of absolute mixing ratios. The differences between the day and night values of the model are in good agreement with the observations although the amplitude of the HO2 diurnal variation is 10–20% lower in the model than in the observations. In particular, the data offered the opportunity to study the reaction ClO+HO2 → HOCl+O2 in the lower mesosphere at 55 km. At this altitude the HOCl night-time variation depends only on this reaction. The result of this analysis points towards a value of the rate constant within the range of the JPL 2006 recommendation and the upper uncertainty limit of the JPL 2011 recommendation at 55 km.