Superconducting Submillimeter-Wave Limb-Emission Sounder Research Articles

Model simulations of chemical effects of sprites in relation with observed HO<sub>2</sub> enhancements over sprite-producing thunderstorms

Abstract. Recently, measurements by the Superconducting Submillimeter-Wave Limb Emission Sounder (SMILES) satellite instrument have been presented which indicate an increase in mesospheric HO2 above sprite-producing thunderstorms. The aim of this paper is to compare these observations to model simulations of chemical sprite effects. A plasma chemistry model in combination with a vertical transport module was used to simulate the impact of a streamer discharge in the altitude range 70–80 km, corresponding to one of the observed sprite events. Additionally, a horizontal transport and dispersion model was used to simulate advection and expansion of the sprite air masses. The model simulations predict a production of hydrogen radicals mainly due to reactions of proton hydrates formed after the electrical discharge. The net effect is a conversion of water molecules into H+OH. This leads to increasing HO2 concentrations a few hours after the electric breakdown. Due to the modelled long-lasting increase in HO2 after a sprite discharge, an accumulation of HO2 produced by several sprites appears possible. However, the number of sprites needed to explain the observed HO2 enhancements is unrealistically large. At least for the lower measurement tangent heights, the production mechanism of HO2 predicted by the model might contribute to the observed enhancements.

The Diurnal Variation in Stratospheric Ozone from MACC Reanalysis, ERA-Interim, WACCM, and Earth Observation Data: Characteristics and Intercomparison

In this study, we compare the diurnal variation in stratospheric ozone of the MACC (Monitoring Atmospheric Composition and Climate) reanalysis, ECMWF Reanalysis Interim (ERA-Interim), and the free-running WACCM (Whole Atmosphere Community Climate Model). The diurnal variation of stratospheric ozone results from photochemical and dynamical processes depending on altitude, latitude, and season. MACC reanalysis and WACCM use similar chemistry modules and calculate a similar diurnal cycle in ozone when it is caused by a photochemical variation. The results of the two model systems are confirmed by observations of the Superconducting Submillimeter-Wave Limb-Emission Sounder (SMILES) experiment and three selected sites of the Network for Detection of Atmospheric Composition Change (NDACC) at Mauna Loa, Hawaii (tropics), Bern, Switzerland (midlatitudes), and Ny-Ålesund, Svalbard (high latitudes). On the other hand, the ozone product of ERA-Interim shows considerably less diurnal variation due to photochemical variations. The global maxima of diurnal variation occur at high latitudes in summer, e.g., near the Arctic NDACC site at Ny-Ålesund, Svalbard. The local OZORAM radiometer observes this effect in good agreement with MACC reanalysis and WACCM. The sensed diurnal variation at Ny-Ålesund is up to 8% (0.4 ppmv) due to photochemical variations in summer and negligible during the dynamically dominated winter. However, when dynamics play a major role for the diurnal ozone variation as in the lower stratosphere (100–20 hPa), the reanalysis models ERA-Interim and MACC which assimilate data from radiosondes and satellites outperform the free-running WACCM. Such a domain is the Antarctic polar winter where a surprising novel feature of diurnal variation is indicated by MACC reanalysis and ERA-Interim at the edge of the polar vortex. This effect accounts for up to 8% (0.4 ppmv) in both model systems. In summary, MACC reanalysis provides a global description of the diurnal variation of stratospheric ozone caused by dynamics and photochemical variations. This is of high interest for ozone trend analysis and other research which is based on merged satellite data or measurements at different local time.

Validation of acetonitrile (CH<sub>3</sub>CN) measurements in the stratosphere and lower mesosphere from the SMILES instrument on the International Space Station

Abstract. Acetonitrile (CH3CN) is a volatile organic compound (VOC) and a potential tracer of biomass burning. We evaluated the capability of using observations derived from the Superconducting Submillimeter-Wave Limb-Emission Sounder (SMILES) on the International Space Station (ISS) to measure CH3CN profiles. The error in a CH3CN vertical profile from the Level-2 research (L2r) product version 3.0.0 was estimated by theoretical error analysis and also compared with other instrumental measurements. We estimated the systematic and random errors to be ∼5.8 ppt (7.8 %) and 25 ppt (60 %), respectively, for a single observation at 15.7 hPa in the tropics, where the CH3CN measurements are enhanced. The major source of systematic error was the pressure-broadening coefficient, and its contribution to the total systematic error was approximately 60 % in the middle stratosphere (15.7–4.8 hPa). The random error decreased to less than 40 % after averaging 10 profiles in the pressure range of 28.8–1.6 hPa. The total error due to uncertainties in other molecular spectroscopic parameters (2.8 ppt) was comparable to that of CH3CN spectroscopic parameters. We compared the SMILES CH3CN profiles with those of the microwave limb sounder (MLS) on the Aura satellite (version 4.2). The SMILES CH3CN values were consistent with those from MLS within the standard deviation (1σ) of the MLS observations. The difference between the SMILES and MLS CH3CN profiles increased with altitude and was within 20–35 ppt (20 %–260 %) at 15.7–1.6 hPa. We observed discrepancies of 5–10 ppt (10 %–30 %) between the SMILES CH3CN profiles observed by different spectrometers, and hence, we do not recommend merging SMILES CH3CN profiles derived from different spectrometers. We found that the SMILES CH3CN volume mixing ratio (VMR) in the upper stratosphere has a seasonal maximum in February.

Potential for the measurement of mesosphere and lower thermosphere (MLT) wind, temperature, density and geomagnetic field with Superconducting Submillimeter-Wave Limb-Emission Sounder 2 (SMILES-2)

Abstract. Submillimeter-Wave Limb-Emission Sounder 2 (SMILES-2) is a satellite mission proposed in Japan to probe the middle and upper atmosphere (20–160 km). The main instrument is composed of 4 K cooled radiometers operating near 0.7 and 2 THz. It could measure the diurnal changes of the horizontal wind above 30 km, temperature above 20 km, ground-state atomic oxygen above 90 km and atmospheric density near the mesopause, as well as abundance of about 15 chemical species. In this study we have conducted simulations to assess the wind, temperature and density retrieval performance in the mesosphere and lower thermosphere (60–110 km) using the radiometer at 760 GHz. It contains lines of water vapor (H2O), molecular oxygen (O2) and nitric oxide (NO) that are the strongest signals measured with SMILES-2 at these altitudes. The Zeeman effect on the O2 line due to the geomagnetic field (B) is considered; otherwise, the retrieval errors would be underestimated by a factor of 2 above 90 km. The optimal configuration for the radiometer’s polarization is found to be vertical linear. Considering a retrieval vertical resolution of 2.5 km, the line-of-sight wind is retrieved with a precision of 2–5 m s−1 up to 90 km and 30 m s−1 at 110 km. Temperature and atmospheric density are retrieved with a precision better than 5 K and 7 % up to 90 km (30 K and 20 % at 110 km). Errors induced by uncertainties on the vector B are mitigated by retrieving it. The retrieval of B is described as a side-product of the mission. At high latitudes, precisions of 30–100 nT on the vertical component and 100–300 nT on the horizontal one could be obtained at 85 and 105 km (vertical resolution of 20 km). SMILES-2 could therefore provide the first measurements of B close to the electrojets' altitude, and the precision is enough to measure variations induced by solar storms in the auroral regions.

Technical note: Reanalysis of Aura MLS chemical observations

Abstract. This paper presents a reanalysis of the atmospheric chemical composition from the upper troposphere to the lower mesosphere from August 2004 to December 2017. This reanalysis is produced by the Belgian Assimilation System for Chemical ObsErvations (BASCOE) constrained by the chemical observations from the Microwave Limb Sounder (MLS) on board the Aura satellite. BASCOE is based on the ensemble Kalman filter (EnKF) method and includes a chemical transport model driven by the winds and temperature from the ERA-Interim meteorological reanalysis. The model resolution is 3.75∘ in longitude, 2.5∘ in latitude and 37 vertical levels from the surface to 0.1 hPa with 25 levels above 100 hPa. The outputs are provided every 6 h. This reanalysis is called BRAM2 for BASCOE Reanalysis of Aura MLS, version 2. Vertical profiles of eight species from MLS version 4 are assimilated and are evaluated in this paper: ozone (O3), water vapour (H2O), nitrous oxide (N2O), nitric acid (HNO3), hydrogen chloride (HCl), chlorine oxide (ClO), methyl chloride (CH3Cl) and carbon monoxide (CO). They are evaluated using independent observations from the Atmospheric Chemistry Experiment Fourier Transform Spectrometer (ACE-FTS), the Michelson Interferometer for Passive Atmospheric Sounding (MIPAS), the Superconducting Submillimeter-Wave Limb-Emission Sounder (SMILES) and N2O observations from a different MLS radiometer than the one used to deliver the standard product and ozonesondes. The evaluation is carried out in four regions of interest where only selected species are evaluated. These regions are (1) the lower-stratospheric polar vortex where O3, H2O, N2O, HNO3, HCl and ClO are evaluated; (2) the upper-stratospheric–lower-mesospheric polar vortex where H2O, N2O, HNO3 and CO are evaluated; (3) the upper troposphere–lower stratosphere (UTLS) where O3, H2O, CO and CH3Cl are evaluated; and (4) the middle stratosphere where O3, H2O, N2O, HNO3, HCl, ClO and CH3Cl are evaluated. In general BRAM2 reproduces MLS observations within their uncertainties and agrees well with independent observations, with several limitations discussed in this paper (see the summary in Sect. 5.5). In particular, ozone is not assimilated at altitudes above (i.e. pressures lower than) 4 hPa due to a model bias that cannot be corrected by the assimilation. MLS ozone profiles display unphysical oscillations in the tropical UTLS, which are corrected by the assimilation, allowing a good agreement with ozonesondes. Moreover, in the upper troposphere, comparison of BRAM2 with MLS and independent observations suggests a positive bias in MLS O3 and a negative bias in MLS H2O. The reanalysis also reveals a drift in MLS N2O against independent observations, which highlights the potential use of BRAM2 to estimate biases between instruments. BRAM2 is publicly available and will be extended to assimilate MLS observations after 2017.

Ice injected into the tropopause by deep convection – Part 1: In the austral convective tropics

Abstract. The contribution of deep convection to the amount of water vapour and ice in the tropical tropopause layer (TTL) from the tropical upper troposphere (UT; around 146 hPa) to the tropopause level (TL; around 100 hPa) is investigated. Ice water content (IWC) and water vapour (WV) measured in the UT and the TL by the Microwave Limb Sounder (MLS; Version 4.2) are compared to the precipitation (Prec) measured by the Tropical Rainfall Measurement Mission (TRMM; Version 007). The two datasets, gridded within 2∘ × 2∘ horizontal bins, have been analysed during the austral convective season, December, January, and February (DJF), from 2004 to 2017. MLS observations are performed at 01:30 and 13:30 local solar time, whilst the Prec dataset is constructed with a time resolution of 1 h. The new contribution of this study is to provide a much more detailed picture of the diurnal variation of ice than is provided by the very limited (two per day) MLS observations. Firstly, we show that IWC represents 70 % and 50 % of the total water in the tropical UT and TL, respectively, and that Prec is spatially highly correlated with IWC in the UT (Pearson's linear coefficient R=0.7). We propose a method that uses Prec as a proxy for deep convection bringing ice up to the UT and TL during the growing stage of convection, in order to estimate the amount of ice injected into the UT and the TL, respectively. We validate the method using ice measurements from the Superconducting Submillimeter-Wave Limb-Emission Sounder (SMILES) during the period DJF 2009–2010. Next, the diurnal cycle of injection of IWC into the UT and the TL by deep convection is calculated by the difference between the maximum and the minimum in the estimated diurnal cycle of IWC in these layers and over selected convective zones. Six tropical highly convective zones have been chosen: South America, South Africa, Pacific Ocean, Indian Ocean, and the Maritime Continent region, split into land (MariCont-L) and ocean (MariCont-O). IWC injection is found to be 2.73 and 0.41 mg m−3 over tropical land in the UT and TL, respectively, and 0.60 and 0.13 mg m−3 over tropical ocean in the UT and TL, respectively. The MariCont-L region has the greatest ice injection in both the UT and TL (3.34 and 0.42–0.56 mg m−3, respectively). The MariCont-O region has less ice injection than MariCont-L (0.91 mg m−3 in the UT and 0.16–0.34 mg m−3 in TL) but has the highest diurnal minimum value of IWC in the TL (0.34–0.37 mg m−3) among all oceanic zones.

Diurnal variation of oxygen isotopic enrichment in asymmetric‐18 ozone observed by the SMILES from space

AbstractAtomic oxygen is a key oxidant for greenhouse gases such as H2O, CH4, and N2O whose amounts are currently increasing in the stratosphere. Ozone photolysis is a major source of atomic oxygen generation. We found, for the first time, that the ozone photolysis of 48O3 and 18O16O16O generated a sharp diurnal variation of δ18OOO in the middle stratosphere (37 km), in contrast to the temporal variation of 48O3. The average isotopic enrichment δ18OOO derived from the Superconducting Submillimeter‐Wave Limb‐Emission Sounder (SMILES) observation was higher during daytime (16.2 ± 3.3%) than at night (13.7 ± 3.6%). Isotopic fractionation effects were simulated for both ozone formation reaction and ozone photolysis with the ozone photolysis contribution estimated to be 80% of the daytime δ18OOO enhancement. Significant solar radiation dependence was observed in the isotopic fractionation of ozone photolysis derived from the SMILES observation and theoretical calculations. These results show that δ18O can be a powerful tool to investigate oxidant chemistry.

Optimal retrieval method to estimate ozone vertical profile in the mesosphere and lower thermosphere (MLT) region from submillimeter-wave limb emission spectra

Spectrum width and intensity of ozone (O3) observed in the MLT region behaves quite differently than in the stratosphere for submillimeter-wave limb emission spectroscopic observation. For example, O3 spectra in the stratosphere are stronger during the day than at night. Conversely, spectra in the MLT region at night are stronger than those occurring during the day due to diurnal variations in O3 behavior. These opposing behaviors cause problems, including oscillations and inaccuracies particularly for O3 vertical profiles in the MLT region retrieved with an application of one retrieval procedure for the entire vertical range (stratosphere to thermosphere). Recently, we developed an optimal retrieval method for O3 in the MLT region for spectra, observed by the Superconducting Submillimeter-Wave Limb-Emission Sounder (SMILES) instrument on the International Space Station. Optimizations were performed for frequency window range, retrieval vertical range, vertical grids, and a priori information for O3 and temperature. Precision and accuracy were evaluated by error analysis and comparisons with previous products. The random error was estimated to be about 5% and 35% in the mesosphere and lower thermosphere, respectively, for nighttime O3 profiles in the MLT region. The total systematic error was about 6% in the MLT region. Certain improvements for both random noise (from 50% to 35%) and systematic error (from 10% to 6%) were obtained. We succeeded in revealing the positive correlation between O3 and ClO at nighttime in the upper mesosphere using the optimized O3 profiles; furthermore, its chemical mechanism was explained quantitatively.

A nudged chemistry‐climate model simulation of chemical constituent distribution at northern high‐latitude stratosphere observed by SMILES and MLS during the 2009/2010 stratospheric sudden warming

AbstractStratospheric sudden warming (SSW) is a dramatic phenomenon of the winter stratosphere in which the distribution of chemical constituents, associated chemical tendency, and transport of chemical constituents differ significantly inside and outside of the polar vortex. In this study, the chemical constituent distributions in the major SSW of 2009/2010 were simulated by the Model for Interdisciplinary Research on Climate 3.2‐Chemistry‐Climate Model (CCM) nudged toward the European Center for Medium‐Range Weather Forecasts‐Interim Re‐Analysis data. The results were compared with Superconducting Submillimeter‐Wave Limb‐Emission Sounder (SMILES) and Microwave Limb Sounder (MLS) observations. In addition, ozone tendency due to ozone transport and chemical ozone loss in the high‐latitude lower stratosphere before and after the SSW was analyzed for the period from 1 January 2010 to 11 February 2010. The evolution and distribution of ozone and HCl inside/outside the polar vortex associated with the vortex shift to the midlatitudes in January are quite similar between SMILES and MLS. Those of ClO are also similar, considering the difference in the local time for the measurement. Analyses of the nudged CCM run indicate that inside the polar vortex at 50 hPa, the ozone concentration increased moderately owing to partial cancelation between the large negative ozone tendency due to chemical ozone destruction and large positive ozone tendency due to horizontal ozone influx from outside of the vortex as well as downward advection. In the region of a high ozone concentration with the same area as that of the polar vortex at 50 hPa, the large increase in ozone was primarily due to a downward advection of ozone. SMILES and MLS observations, nudged CCM simulations, and ozone tendency analyses revealed a highly longitudinal dependent ozone tendency at high latitudes during the SSW.

SMILES observations of mesospheric ozone during the solar eclipse

AbstractThe Superconducting Submillimeter‐Wave Limb‐Emission Sounder (SMILES) successfully observed vertical distributions of ozone (O3) concentration in the middle atmosphere during the annular solar eclipse that occurred on 15 January 2010. In the mesosphere, where the photochemical lifetime of O3 is relatively short (approximately 100 s), altitude‐dependent changes in O3 concentration under reduced solar radiation and their temporal variations were clearly observed as a function of the eclipse obscuration. This study reports the vertical distributions of mesospheric O3 during a solar eclipse event and analyzes theoretically the eclipse‐induced changes. We show that simple analytical expressions for O3 concentration, which assume that O3 and O are in a photochemically steady state, can be used to describe the O3 concentration under reduced solar radiation. The SMILES data obtained during the eclipse provide a unique opportunity to test our current understanding of mesospheric O3 photochemistry.

Stratospheric and mesospheric HO<sub>2</sub> observations from the Aura Microwave Limb Sounder

Abstract. This study introduces stratospheric and mesospheric hydroperoxyl radical (HO2) estimates from the Aura Microwave Limb Sounder (MLS) using an offline retrieval (i.e. run separately from the standard MLS algorithm). This new data set provides two daily zonal averages, one during daytime from 10 to 0.0032 hPa (using day-minus-night differences between 10 and 1 hPa to ameliorate systematic biases) and one during nighttime from 1 to 0.0032 hPa. The vertical resolution of this new data set varies from about 4 km at 10 hPa to around 14 km at 0.0032 hPa. A description of the methodology and an error analysis are presented. Comparisons against the Whole Atmosphere Community Climate Model (WACCM), the Superconducting Submillimeter-Wave Limb-Emission Sounder (SMILES) and the Far Infrared Spectrometer (FIRS-2) measurements, as well as photochemical simulations, demonstrate the robustness of the retrieval and indicate that the retrieval is sensitive enough to detect mesospheric HO2 layers during both day and night. This new data set is the first long-term HO2 stratospheric and mesospheric satellite record and it provides needed constraints to help resolve the O3 deficit problem and the "HOx dilemma".

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.

The use of SMILES data to study ozone loss in the Arctic winter 2009/2010 and comparison with Odin/SMR data using assimilation techniques

Abstract. The Superconducting Submillimeter-Wave Limb-Emission Sounder (SMILES) on board the International Space Station observed ozone in the stratosphere with high precision from October 2009 to April 2010. Although SMILES measurements only cover latitudes from 38° S to 65° N, the combination of data assimilation methods and an isentropic advection model allows us to quantify the ozone depletion in the 2009/2010 Arctic polar winter by making use of the instability of the polar vortex in the northern hemisphere. Ozone data from both SMILES and Odin/SMR (Sub-Millimetre Radiometer) for the winter were assimilated into the Dynamical Isentropic Assimilation Model for OdiN Data (DIAMOND). DIAMOND is an off-line wind-driven transport model on isentropic surfaces. Wind data from the operational analyses of the European Centre for Medium- Range Weather Forecasts (ECMWF) were used to drive the model. In this study, particular attention is paid to the cross isentropic transport of the tracer in order to accurately assess the ozone loss. The assimilated SMILES ozone fields agree well with the limitation of noise induced variability within the SMR fields despite the limited latitude coverage of the SMILES observations. Ozone depletion has been derived by comparing the ozone field acquired by sequential assimilation with a passively transported ozone field initialized on 1 December 2009. Significant ozone loss was found in different periods and altitudes from using both SMILES and SMR data: The initial depletion occurred at the end of January below 550 K with an accumulated loss of 0.6–1.0 ppmv (approximately 20%) by 1 April. The ensuing loss started from the end of February between 575 K and 650 K. Our estimation shows that 0.8–1.3 ppmv (20–25 %) of O3 has been removed at the 600 K isentropic level by 1 April in volume mixing ratio (VMR).

Overview and sample applications of SMILES and Odin-SMR retrievals of upper tropospheric humidity and cloud ice mass

Abstract. Retrievals of cloud ice mass and humidity from the Superconducting Submillimeter-Wave Limb-Emission Sounder (SMILES) and the Odin-SMR (Sub-Millimetre Radiometer) limb sounder are presented and example applications of the data are given. SMILES data give an unprecedented view of the diurnal variation of cloud ice mass. Mean regional diurnal cycles are reported and compared to some global climate models. Some improvements in the models regarding diurnal timing and relative amplitude were noted, but the models' mean ice mass around 250 hPa is still low compared to the observations. The influence of the ENSO (El Niño–Southern Oscillation) state on the upper troposphere is demonstrated using 12 years of Odin-SMR data. The same retrieval scheme is applied for both sensors, and gives low systematic differences between the two data sets. A special feature of this Bayesian retrieval scheme, of Monte Carlo integration type, is that values are produced for all measurements but for some atmospheric states retrieved values only reflect a priori assumptions. However, this "all-weather" capability allows a direct statistical comparison to model data, in contrast to many other satellite data sets. Another strength of the retrievals is the detailed treatment of "beam filling" that otherwise would cause large systematic biases for these passive cloud ice mass retrievals. The main retrieval inputs are spectra around 635/525 GHz from tangent altitudes below 8/9 km for SMILES/Odin-SMR, respectively. For both sensors, the data cover the upper troposphere between 30° S and 30° N. Humidity is reported as both relative humidity and volume mixing ratio. The vertical coverage of SMILES is restricted to a single layer, while Odin-SMR gives some profiling capability between 300 and 150 hPa. Ice mass is given as the partial ice water path above 260 hPa, but for Odin-SMR ice water content, estimates are also provided. Besides a smaller contrast between most dry and wet cases, the agreement with Aura MLS (Microwave Limb Sounder) humidity data is good. In terms of tropical mean humidity, all three data sets agree within 3.5 %RHi. Mean ice mass is about a factor of 2 lower compared to CloudSat. This deviation is caused by the fact that different particle size distributions are assumed, combined with saturation and a priori influences in the SMILES and Odin-SMR data.

Diurnal variations of stratospheric ozone measured by ground-based microwave remote sensing at the Mauna Loa NDACC site: measurement validation and GEOSCCM model comparison

Abstract. There is presently renewed interest in diurnal variations of stratospheric and mesospheric ozone for the purpose of supporting homogenization of records of various ozone measurements that are limited by the technique employed to being made at certain times of day. We have made such measurements for 19 years using a passive microwave remote sensing technique at the Mauna Loa Observatory (MLO) in Hawaii, which is a primary station in the Network for Detection of Atmospheric Composition Change (NDACC). We have recently reprocessed these data with hourly time resolution to study diurnal variations. We inspected differences between pairs of the ozone spectra (e.g., day and night) from which the ozone profiles are derived to determine the extent to which they may be contaminated by diurnally varying systematic instrumental or measurement effects. These are small, and we have reduced them further by selecting data that meet certain criteria that we established. We have calculated differences between profiles measured at different times: morning–night, afternoon–night, and morning–afternoon and have intercompared these with like profiles derived from the Aura Microwave Limb Sounder (Aura-MLS), the Upper Atmosphere Research Satellite Microwave Limb Sounder (UARS-MLS), the Superconducting Submillimeter-Wave Limb-Emission Sounder (SMILES), and Solar Backscatter Ultraviolet version 2 (SBUV/2) measurements. Differences between averages of coincident profiles are typically < 1.5% of typical nighttime values over most of the covered altitude range with some exceptions. We calculated averages of ozone values for each hour from the Mauna Loa microwave data, and normalized these to the average for the first hour after midnight for comparison with corresponding values calculated with the Goddard Earth Observing System Chemistry Climate Model (GEOSCCM). We found that the measurements and model output mostly agree to better than 1.5% of the midnight value, with one noteworthy exception: The measured morning–night values are significantly (2–3 %) higher than the modeled ones from 3.2 to 1.8 hPa (~39–43 km), and there is evidence that the measured values are increasing compared to the modeled values before sunrise in this region.

Vertical profile of δ<sup>18</sup>OOO from the middle stratosphere to lower mesosphere from SMILES spectra

Abstract. Ozone is known to have large oxygen isotopic enrichments of about 10% in the middle stratosphere; however, there have been no reports of ozone isotopic enrichments above the middle stratosphere. We derived an enrichment δ18OOO in the stratosphere and the lower mesosphere from observations of the Superconducting Submillimeter-Wave Limb-Emission Sounder (SMILES) onboard the International Space Station (ISS) using a retrieval algorithm optimized for the isotopic ratio. The retrieval algorithm includes (i) an a priori covariance matrix constrained by oxygen isotopic ratios in ozone, (ii) an optimization of spectral windows for ozone isotopomers and isotopologues, and (iii) common tangent height information for all windows. The δ18OOO by averaging the SMILES measurements at the latitude range of 20 to 40° N from February to March in 2010 with solar zenith angle < 80° was 13% (at 32 km) with the systematic error of about 5%. SMILES and past measurements were in good agreement, with δ18OOO increasing with altitude between 30 and 40 km. The vertical profile of δ18OOO obtained in this study showed an increase and a decrease with altitude in the stratosphere and mesosphere, respectively. The δ18OOO peak, 18%, is found at the stratopause. The δ18OOO has a positive correlation with temperature in the range of 220–255 K, indicating that temperature can be a dominant factor to control the vertical profile of δ18OOO in the stratosphere and mesosphere. This is the first report of the observation of δ18OOO over a wide altitude range extending from the stratosphere to the mesosphere (28–57 km).

Direct estimation of the rate constant of the reaction ClO + HO<sub>2</sub> → HOCl + O<sub>2</sub> from SMILES atmospheric observations

Abstract. Diurnal variations of ClO, HO2, and HOCl were simultaneously observed by the Superconducting Submillimeter-Wave Limb-Emission Sounder (SMILES) between 12 October 2009 and 21 April 2010. These were the first global observations of the diurnal variation of HOCl in the upper atmosphere. A major reaction for the production of HOCl is ClO + HO2 → HOCl + O2 (Reaction (R1)) in extra-polar regions. A model study suggested that in the mesosphere, this is the only reaction influencing the amount of HOCl during the night. The evaluation of the pure reaction period, when only Reaction (R1) occurred in the Cly chemical system, was performed by checking the consistency of the HOCl production rate with the ClO loss rate from SMILES observation data. It turned out that the SMILES data at the pressure level of 0.28 hPa (about 58 km) in the autumn mid-latitude region (20–40°, February–April 2010) during night (between modified local time 18:30 and 04:00) were suitable for the estimation of the rate constant, k1. The rate constant obtained from SMILES observations was k1(245 K) = (7.75 ± 0.25) × 10−12 cm3 molecule−1 s−1. This result is consistent with results from a laboratory experiment and ab initio calculations for similar low-pressure conditions.

Comparison of SMILES ClO profiles with satellite, balloon-borne and ground-based measurements

Abstract. We evaluate the quality of ClO profiles derived from the Superconducting Submillimeter-Wave Limb-Emission Sounder (SMILES) on the International Space Station (ISS). Version 2.1.5 of the level-2 product generated by the National Institute of Information and Communications Technology (NICT) is the subject of this study. Based on sensitivity studies, the systematic error was estimated as 5–10 pptv at the pressure range of 80–20 hPa, 35 pptv at the ClO peak altitude (~ 4 hPa), and 5–10 pptv at pressures ≤ 0.5 hPa for daytime mid-latitude conditions. For nighttime measurements, a systematic error of 8 pptv was estimated for the ClO peak altitude (~ 2 hPa). The SMILES NICT v2.1.5 ClO profiles agree with those derived from another level-2 processor developed by the Japan Aerospace Exploration Agency (JAXA) within the bias uncertainties, except for the nighttime measurements in the low and middle latitude regions where the SMILES NICT v2.1.5 profiles have a negative bias of ~ 30 pptv in the lower stratosphere. This bias is considered to be due to the use of a limited spectral bandwidth in the retrieval process of SMILES NICT v2.1.5, which makes it difficult to distinguish between the weak ClO signal and wing contributions of spectral features outside the bandwidth. In the middle and upper stratosphere outside the polar regions, no significant systematic bias was found for the SMILES NICT ClO profile with respect to data sets from other instruments such as the Aura Microwave Limb Sounder (MLS), the Odin Sub-Millimetre Radiometer (SMR), the Envisat Michelson Interferometer for Passive Atmospheric Sounding (MIPAS), and the ground-based radiometer at Mauna Kea, which demonstrates the scientific usability of the SMILES ClO data including the diurnal variations. Inside the chlorine-activated polar vortex, the SMILES NICT v2.1.5 ClO profiles show larger volume mixing ratios by 0.4 ppbv (30%) at 50 hPa compared to those of the JAXA processed profiles. This discrepancy is also considered to be an effect of the limited spectral bandwidth in the retrieval processing. We also compared the SMILES NICT ClO profiles of chlorine-activated polar vortex conditions with those measured by the balloon-borne instruments: Terahertz and submillimeter Limb Sounder (TELIS) and the MIPAS-balloon instrument (MIPAS-B). In conclusion, the SMILES NICT v2.1.5 ClO data can be used at pressures ≤ ~30 hPa for scientific analysis.

Comparison of ozone profiles between Superconducting Submillimeter‐Wave Limb‐Emission Sounder and worldwide ozonesonde measurements

AbstractWe compared ozone profiles measured by the Superconducting Submillimeter‐Wave Limb‐Emission Sounder (SMILES) with those taken at worldwide ozonesonde stations. To assess the quality of the SMILES version 2.3 ozone data for 16–30 km, 601 ozonesonde profiles were compared with the coincident SMILES ozone profiles. The agreement between SMILES and ozonesonde measurements was generally good within 5%–7% for 18–30 km at middle and high latitudes but degraded below 18 km. At low latitudes, however, the SMILES ozone data showed larger values (~6%–15% for 20–26 km) than those at middle and high latitudes. To explain this bias, we explored some possible issues in the ozonesonde measurement system. One possibility is due to a pressure bias in radiosonde measurements with a pressure sensor, but it would be within a few percent. We also examined an issue of the ozonesonde's response time. The response time was estimated from ozonesonde measurements with ascending and descending profiles showing clear difference, by using the time lag correction method to minimize the difference between them. Our estimation shows 28 s on average which is a similar value derived by prelaunch preparation. By applying this correction to the original profiles, we found a negative bias of the ascending ozonesonde measurement more than 7% at 20 km in the equatorial latitude where the vertical gradient of ozone is steep. The corrected ozonesonde profiles showed better agreement with the SMILES data. We suggest that the response time of ozonesondes could create a negative bias, particularly in the lower stratosphere at equatorial latitudes.

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.