Search

Polar stratospheric clouds (PSCs) are an important component of ozone chemistry in polar regions. Studying the ozone-depleting processes requires a precise description of PSCs on a long-term basis. Although satellite observations already yield high spatial coverage, continuous ground-based measurements covering long time periods can be a valuable complement. In this study, differential optical absorption spectroscopy (DOAS) instruments are used to investigate the occurrence of PSCs based on the so-called colour index (CI), i.e. the colour of the zenith sky. Defined as the ratio between the observed intensities of scattered sunlight at two wavelengths, it provides a method to detect PSCs during twilight even in the presence of tropospheric clouds. We present data from instruments at the German research station Neumayer, Antarctica (71∘ S, 8∘ W), as well as Kiruna, Sweden (68∘ N, 20∘ E), which have been in operation for more than 20 years. For a comprehensive interpretation of the measurement data, the well-established radiative transfer model McArtim is used and radiances of scattered sunlight are simulated at several wavelengths for different solar zenith angles and various atmospheric conditions. The aim is to improve and evaluate the potential of this method. It is then used to infer the seasonal cycle and the variability of PSC occurrence throughout the time series measured in both hemispheres. A good agreement is found to satellite retrievals with deviations particularly in spring. The unexpectedly high signal observed in the DOAS data during springtime suggests the influence of volcanic aerosol. This is also indicated by enhanced aerosol extinction as seen from OMPS (Ozone Mapping and Profiler Suite) data but is not captured by other PSC climatologies. The presented approach allows the detection of PSCs for various atmospheric conditions not only for individual case studies but over entire time series, which is a decisive advance compared to previous work on the PSC detection by ground-based instruments. Apart from the interannual variability, no significant trend is detected for either measurement station. The averaged PSC relative frequency amounts to about 37 % above the Neumayer station and about 18 % above Kiruna.

In this study, an extension on the previously reported status of the COllaborative Carbon Column Observing Network's (COCCON) calibration procedures incorporating refined methods is presented. COCCON is a global network of portable Bruker EM27/SUN FTIR spectrometers for deriving column-averaged atmospheric abundances of greenhouse gases. The original laboratory open-path lamp measurements for deriving the instrumental line shape (ILS) of the spectrometer from water vapour lines have been refined and extended to the secondary detector channel incorporated in the EM27/SUN spectrometer for detection of carbon monoxide (CO). The refinements encompass improved spectroscopic line lists for the relevant water lines and a revision of the laboratory pressure measurements used for the analysis of the spectra. The new results are found to be in good agreement with those reported by Frey et al. (2019) and discussed in detail. In addition, a new calibration cell for ILS measurements was designed, constructed and put into service. Spectrometers calibrated since January 2020 were tested using both methods for ILS characterization, open-path (OP) and cell measurements. We demonstrate that both methods can detect the small variations in ILS characteristics between different spectrometers, but the results of the cell method indicate a systematic bias of the OP method. Finally, a revision and extension of the COCCON network instrument-to-instrument calibration factors for XCO2, XCO and XCH4 is presented, incorporating 47 new spectrometers (of 83 in total by now). This calibration is based on the reference EM27/SUN spectrometer operated by the Karlsruhe Institute of Technology (KIT) and spectra collected by the collocated TCCON station Karlsruhe. Variations in the instrumental characteristics of the reference EM27/SUN from 2014 to 2017 were detected, probably arising from realignment and the dual-channel upgrade performed in early 2018. These variations are considered in the evaluation of the instrument-specific calibration factors in order to keep all tabulated calibration results consistent.

Here we present a new retrieval algorithm of the slant column densities (SCDs) of chlorine dioxide (OClO) by differential optical absorption spectroscopy (DOAS) from measurements performed by TROPOspheric Monitoring Instrument (TROPOMI) on board of Sentinel-5P satellite. To achieve a substantially improved accuracy, which is especially important for OClO observations, accounting for absorber and pseudo absorber structures in optical depth even of the order of 10−4 is important. Therefore, in comparison to existing retrievals, we include several additional fit parameters by accounting for spectral effects like the temperature dependency of the Ring effect and Ring absorption effects, a higher-order term for the OClO SCD dependency on wavelength and accounting for the BrO absorption. We investigate the performance of different retrieval settings by an error analysis with respect to random variations, large-scale systematic variations as a function of solar zenith angle and also more localized systematic variations by a novel application of an autocorrelation analysis. The retrieved TROPOMI OClO SCDs show a very good agreement with ground-based zenith sky measurements and are correlated well with preliminary data of the operational TROPOMI OClO retrieval algorithm currently being developed as part of ESA's Sentinel-5P+ Innovation project.

In this paper, we compare column-averaged dry-air mole fractions of water vapor (XH2O) retrievals from the COllaborative Carbon Column Observing Network (COCCON) with retrievals from two co-located high-resolution Fourier transform infrared (FTIR) spectrometers as references at two boreal sites, Kiruna, Sweden, and Sodankylä, Finland, from 6 March 2017 to 20 September 2019. In the framework of the Network for the Detection of Atmospheric Composition Change (NDACC), an FTIR spectrometer is operated at Kiruna. The H2O product derived from these observations has been generated with the MUlti-platform remote Sensing of Isotopologues for investigating the Cycle of Atmospheric water (MUSICA) processor. In Sodankylä, a Total Carbon Column Observing Network (TCCON) spectrometer is operated, and the official XH2O data as provided by TCCON are used for this study. The datasets are in good overall agreement, with COCCON data showing a wet bias of (49.20±58.61) ppm ((3.33±3.37) %, R2=0.9992) compared with MUSICA NDACC and (56.32±45.63) ppm ((3.44±1.77) %, R2=0.9997) compared with TCCON. Furthermore, the a priori H2O volume mixing ratio (VMR) profiles (MAP) used as a priori information in the TCCON retrievals (also adopted for COCCON retrievals) are evaluated with respect to radiosonde (Vaisala RS41) profiles at Sodankylä. The MAP and radiosonde profiles show similar shapes and a good linear correlation of integrated XH2O, indicating that MAP is a reasonable approximation of the true atmospheric state and an appropriate choice for the scaling retrieval methods as applied by COCCON and TCCON. COCCON shows a reduced dry bias (−14.96 %) in comparison with TCCON (−19.08 %) with respect to radiosonde XH2O. Finally, we investigate the quality of satellite data at high latitudes. For this purpose, the COCCON XH2O is compared with retrievals from the Infrared Atmospheric Sounding Interferometer (IASI) generated with the MUSICA processor (MUSICA IASI) and with retrievals from the TROPOspheric Monitoring Instrument (TROPOMI). Both paired datasets generally show good agreement and similar correlations at the two sites. COCCON measures 4.64 % less XH2O at Kiruna and 3.36 % less at Sodankylä with respect to MUSICA IASI, whereas COCCON measures 9.71 % more XH2O at Kiruna and 7.75 % more at Sodankylä compared with TROPOMI. Our study supports the assumption that COCCON also delivers a well-characterized XH2O data product. This emphasizes that this approach might complement the TCCON network with respect to satellite validation efforts. This is the first published study where COCCON XH2O has been compared with MUSICA NDACC and TCCON retrievals and has been used for MUSICA IASI and TROPOMI validation.

Although optical components in Fourier transform infrared (FTIR) spectrometers are preferably wedged, in practice, infrared spectra typically suffer from the effects of optical resonances (“channeling”) affecting the retrieval of weakly absorbing gases. This study investigates the level of channeling of each FTIR spectrometer within the Network for the Detection of Atmospheric Composition Change (NDACC). Dedicated spectra were recorded by more than 20 NDACC FTIR spectrometers using a laboratory mid-infrared source and two detectors. In the indium antimonide (InSb) detector domain (1900–5000 cm−1), we found that the amplitude of the most pronounced channeling frequency amounts to 0.1 ‰ to 2.0 ‰ of the spectral background level, with a mean of (0.68±0.48) ‰ and a median of 0.60 ‰. In the mercury cadmium telluride (HgCdTe) detector domain (700–1300 cm−1), we find even stronger effects, with the largest amplitude ranging from 0.3 ‰ to 21 ‰ with a mean of (2.45±4.50) ‰ and a median of 1.2 ‰. For both detectors, the leading channeling frequencies are 0.9 and 0.11 or 0.23 cm−1 in most spectrometers. The observed spectral frequencies of 0.11 and 0.23 cm−1 correspond to the optical thickness of the beam splitter substrate. The 0.9 cm−1 channeling is caused by the air gap in between the beam splitter and compensator plate. Since the air gap is a significant source of channeling and the corresponding amplitude differs strongly between spectrometers, we propose new beam splitters with the wedge of the air gap increased to at least 0.8∘. We tested the insertion of spacers in a beam splitter's air gap to demonstrate that increasing the wedge of the air gap decreases the 0.9 cm−1 channeling amplitude significantly. A wedge of the air gap of 0.8∘ reduces the channeling amplitude by about 50 %, while a wedge of about 2∘ removes the 0.9 cm−1 channeling completely. This study shows the potential for reducing channeling in the FTIR spectrometers operated by the NDACC, thereby increasing the quality of recorded spectra across the network.

We compare the atmospheric column-averaged dry-air mole fractions of carbon dioxide (XCO2) and methane (XCH4) measured with a pair of COllaborative Carbon Column Observing Network (COCCON) spectrometers at Kiruna and Sodankylä (boreal areas). We compare model data provided by the Copernicus Atmosphere Monitoring Service (CAMS) between 2017 and 2019 with XCH4 data from the recently launched Sentinel-5 Precursor (S5P) satellite between 2018 and 2019. In addition, measured and modeled gradients of XCO2 and XCH4 (ΔXCO2 and ΔXCH4) on regional scales are investigated. Both sites show a similar and very good correlation between COCCON retrievals and the modeled CAMS XCO2 data, while CAMS data are biased high with respect to COCCON by 3.72 ppm (±1.80 ppm) in Kiruna and 3.46 ppm (±1.73 ppm) in Sodankylä on average. For XCH4, CAMS values are higher than the COCCON observations by 0.33 ppb (±11.93 ppb) in Kiruna and 7.39 ppb (±10.92 ppb) in Sodankylä. In contrast, the S5P satellite generally measures lower atmospheric XCH4 than the COCCON spectrometers, with a mean difference of 9.69 ppb (±20.51 ppb) in Kiruna and 3.36 ppb (±17.05 ppb) in Sodankylä. We compare the gradients of XCO2 and XCH4 (ΔXCO2 and ΔXCH4) between Kiruna and Sodankylä derived from CAMS analysis and COCCON and S5P measurements to study the capability of detecting sources and sinks on regional scales. The correlations in ΔXCO2 and ΔXCH4 between the different datasets are generally smaller than the correlations in XCO2 and XCH4 between the datasets at either site. The ΔXCO2 values predicted by CAMS are generally higher than those observed with COCCON with a slope of 0.51. The ΔXCH4 values predicted by CAMS are mostly higher than those observed with COCCON with a slope of 0.65, covering a larger dataset than the comparison between S5P and COCCON. When comparing CAMS ΔXCH4 with COCCON ΔXCH4 only in S5P overpass days (slope = 0.53), the correlation is close to that between S5P and COCCON (slope = 0.51). CAMS, COCCON, and S5P predict gradients in reasonable agreement. However, the small number of observations coinciding with S5P limits our ability to verify the performance of this spaceborne sensor. We detect no significant impact of ground albedo and viewing zenith angle on the S5P results. Both sites show similar situations with the average ratios of XCH4 (S5P/COCCON) of 0.9949±0.0118 in Kiruna and 0.9953±0.0089 in Sodankylä. Overall, the results indicate that the COCCON instruments have the capability of measuring greenhouse gas (GHG) gradients on regional scales, and observations performed with the portable spectrometers can contribute to inferring sources and sinks and to validating spaceborne greenhouse gas sensors. To our knowledge, this is the first published study using COCCON spectrometers for the validation of XCH4 measurements collected by S5P.

This work presents the methane (CH4) and nitrous oxide (N2O) products as generated by the IASI (Infrared Atmospheric Sounding Interferometer) processor developed during the project MUSICA (MUlti-platform remote Sensing of Isotopologues for investigating the Cycle of Atmospheric water). The processor retrieves CH4 and N2O with different water vapour and water vapour isotopologues (as well as HNO3) and uses a single a priori data set for all the retrievals (no variation in space and time). Firstly, the characteristics and errors of the products are analytically described. Secondly, the products are comprehensively evaluated by comparisons to the following reference data measured by different techniques and from different platforms as follows: (1) aircraft CH4 and N2O profiles from the five HIAPER Pole-to-Pole Observation (HIPPO) missions; (2) continuous in situ CH4 and N2O observations performed between 2007 and 2017 at subtropical and mid-latitude high-mountain observatories (Izaña Atmospheric Observatory and Jungfraujoch, respectively) in the framework of the WMO–GAW (World Meteorological Organization–Global Atmosphere Watch) programme; (3) ground-based FTIR (Fourier-transform infrared spectrometer) measurements made between 2007 and 2017 in the framework of the NDACC (Network for the Detection of Atmospheric Composition Change) at the subtropical Izaña Atmospheric Observatory, the mid-latitude station of Karlsruhe and the Kiruna polar site.The theoretical estimations and the comparison studies suggest a precision for the N2O and CH4 retrieval products of about 1.5–3 % and systematic errors due to spectroscopic parameters of about 2 %. The MUSICA IASI CH4 data offer a better sensitivity than N2O data. While for the latter the sensitivity is mainly limited to the UTLS (upper troposphere–lower stratosphere) region, for CH4 we are able to prove that at low latitudes the MUSICA IASI processor can detect variations that take place in the free troposphere independently from the variations in the UTLS region. We demonstrate that the MUSICA IASI data qualitatively capture the CH4 gradients between low and high latitudes and between the Southern Hemisphere and Northern Hemisphere; however, we also find an inconsistency between low- and high-latitude CH4 data of up to 5 %. The N2O latitudinal gradients are very weak and cannot be detected. We make comparisons over a 10-year time period and analyse the agreement with the reference data on different timescales. The MUSICA IASI data can detect day-to-day signals (only in the UTLS), seasonal cycles and long-term evolution (in the UTLS and for CH4 also in the free troposphere) similar to the reference data; however, there are also inconsistencies in the long-term evolution connected to inconsistencies in the used atmospheric temperature a priori data.Moreover, we present a method for analytically describing the a posteriori-calculated logarithmic-scale difference of the CH4 and N2O retrieval estimates. By correcting errors that are common in the CH4 and N2O retrieval products, the a posteriori-calculated difference can be used for generating an a posteriori-corrected CH4 product with a theoretically better precision than the original CH4 retrieval products. We discuss and evaluate two different approaches for such a posteriori corrections. It is shown that the correction removes the inconsistencies between low and high latitudes and enables the detection of day-to-day signals also in the free troposphere. Furthermore, they reduce the impact of short-term atmospheric dynamics, which is an advantage, because respective signals are presumably hardly comparable to model data. The approach that affects the correction solely on the scales on which the errors dominate is identified as the most efficient, because it reduces the inconsistencies and errors without removing measurable real atmospheric signals. We give a brief outlook on a possible usage of this a posteriori-corrected MUSICA IASI CH4 product in combination with inverse modelling.

We investigate the reliability of using trace gas measurements from remote sensing instruments to infer polar atmospheric descent rates during winter within 46–86 km altitude. Using output from the Specified Dynamics Whole Atmosphere Community Climate Model (SD-WACCM) between 2008 and 2014, tendencies of carbon monoxide (CO) volume mixing ratios (VMRs) are used to assess a common assumption of dominant vertical advection of tracers during polar winter. The results show that dynamical processes other than vertical advection are not negligible, meaning that the transport rates derived from trace gas measurements do not represent the mean descent of the atmosphere. The relative importance of vertical advection is lessened, and exceeded by other processes, during periods directly before and after a sudden stratospheric warming, mainly due to an increase in eddy transport. It was also found that CO chemistry cannot be ignored in the mesosphere due to the night-time layer of OH at approximately 80 km altitude. CO VMR profiles from the Kiruna Microwave Radiometer and the Microwave Limb Sounder were compared to SD-WACCM output, and show good agreement on daily and seasonal timescales. SD-WACCM CO profiles are combined with the CO tendencies to estimate errors involved in calculating the mean descent of the atmosphere from remote sensing measurements. The results indicate errors on the same scale as the calculated descent rates, and that the method is prone to a misinterpretation of the direction of air motion. The true rate of atmospheric descent is seen to be masked by processes, other than vertical advection, that affect CO. We suggest an alternative definition of the rate calculated using remote sensing measurements: not as the mean descent of the atmosphere, but as an effective rate of vertical transport for the trace gas under observation.

This paper presents new atmospheric ozone concentration profiles retrieved from measurements made with two ground-based millimetre-wave radiometers in Kiruna, Sweden. The instruments are the Kiruna Microwave Radiometer (KIMRA) and the Millimeter wave Radiometer 2 (MIRA 2). The ozone concentration profiles are retrieved using an optimal estimation inversion technique, and they cover an altitude range of ∼ 16–54 km, with an altitude resolution of, at best, 8 km. The KIMRA and MIRA 2 measurements are compared to each other, to measurements from balloon-borne ozonesonde measurements at Sodankylä, Finland, and to measurements made by the Microwave Limb Sounder (MLS) aboard the Aura satellite. KIMRA has a correlation of 0.82, but shows a low bias, with respect to the ozonesonde data, and MIRA 2 shows a smaller magnitude low bias and a 0.98 correlation coefficient. Both radiometers are in general agreement with each other and with MLS data, showing high correlation coefficients, but there are differences between measurements that are not explained by random errors. An oscillatory bias with a peak of approximately ±1 ppmv is identified in the KIMRA ozone profiles over an altitude range of ∼ 18–35 km, and is believed to be due to baseline wave features that are present in the spectra. A time series analysis of KIMRA ozone for winters 2008–2013 shows the existence of a local wintertime minimum in the ozone profile above Kiruna. The measurements have been ongoing at Kiruna since 2002 and late 2012 for KIMRA and MIRA 2, respectively.

Within the NDACC (Network for the Detection of Atmospheric Composition Change), more than 20 FTIR (Fourier-transform infrared) spectrometers, spread worldwide, provide long-term data records of many atmospheric trace gases. We present a method that uses measured and modelled XCO2 for assessing the consistency of these NDACC data records. Our XCO2 retrieval setup is kept simple so that it can easily be adopted for any NDACC/FTIR-like measurement made since the late 1950s. By a comparison to coincident TCCON (Total Carbon Column Observing Network) measurements, we empirically demonstrate the useful quality of this suggested NDACC XCO2 product (empirically obtained scatter between TCCON and NDACC is about 4‰ for daily mean as well as monthly mean comparisons, and the bias is 25‰). Our XCO2 model is a simple regression model fitted to CarbonTracker results and the Mauna Loa CO2 in situ records. A comparison to TCCON data suggests an uncertainty of the model for monthly mean data of below 3‰. We apply the method to the NDACC/FTIR spectra that are used within the project MUSICA (multi-platform remote sensing of isotopologues for investigating the cycle of atmospheric water) and demonstrate that there is a good consistency for these globally representative set of spectra measured since 1996: the scatter between the modelled and measured XCO2 on a yearly time scale is only 3‰.

Within the project MUSICA (MUlti-platform remote Sensing of Isotopologues for investigating the Cycle of Atmospheric water) ground- and space-based remote sensing as well as in situ data sets of tropospheric water vapour isotopologues are provided. The space-based remote-sensing data set is produced from spectra measured by the IASI (Infrared Atmospheric Sounding Interferometer) sensor and is potentially available on a global scale. Here, we present the MUSICA IASI data for three different geophysical locations (subtropics, midlatitudes, and Arctic), and we provide a comprehensive characterisation of the complex nature of such space-based isotopologue remote-sensing products. The quality assessment study is complemented by a comparison to MUSICA's ground-based FTIR (Fourier Transform InfraRed) remote-sensing data retrieved from the spectra recorded at three different locations within the framework of NDACC (Network for the Detection of Atmospheric Composition Change). We confirm that IASI is able to measure tropospheric H2O profiles with a vertical resolution of about 4 km and a random error of about 10%. In addition IASI can observe middle tropospheric δD that adds complementary value to IASI's middle tropospheric H2O observations. Our study presents theoretical and empirical proof that IASI has the capability for a global observation of middle tropospheric water vapour isotopologues on a daily timescale and at a quality that is sufficiently high for water cycle research purposes.

Carbon monoxide (CO) is retrieved daily and globally from space-borne IASI radiance spectra using the Fast Optimal Retrievals on Layers for IASI (FORLI) software developed at the Université Libre de Bruxelles (ULB). The IASI CO total column product for 2008 from the most recent FORLI retrieval version (20100815) is evaluated using correlative CO profile products retrieved from ground-based solar absorption Fourier transform infrared (FTIR) observations at the following FTIR spectrometer sites from the Network for the Detection of Atmospheric Composition Change (NDACC): Ny-Ålesund, Kiruna, Bremen, Jungfraujoch, Izaña and Wollongong. In order to have good statistics for the comparisons, we included all IASI data from the same day, within a 100 km radius around the ground-based stations. The individual ground-based data were adjusted to the lowest altitude of the co-located IASI CO profiles. To account for the different vertical resolutions and sensitivities of the ground-based and satellite measurements, the averaging kernels associated with the various retrieved products have been used to properly smooth coincident data products. It has been found that the IASI CO total column products compare well on average with the co-located ground-based FTIR total columns at the selected NDACC sites and that there is no significant bias for the mean values at all stations.

We compare measurements of integrated water vapour (IWV) over a subarctic site (Kiruna, Northern Sweden) from five different sensors and retrieval methods: Radiosondes, Global Positioning System (GPS), ground-based Fourier-transform infrared (FTIR) spectrometer, ground-based microwave radiometer, and satellite-based microwave radiometer (AMSU-B). Additionally, we compare also to ERA-Interim model reanalysis data. GPS-based IWV data have the highest temporal coverage and resolution and are chosen as reference data set. All datasets agree reasonably well, but the ground-based microwave instrument only if the data are cloud-filtered. We also address two issues that are general for such intercomparison studies, the impact of different lower altitude limits for the IWV integration, and the impact of representativeness error. We develop methods for correcting for the former, and estimating the random error contribution of the latter. A literature survey reveals that reported systematic differences between different techniques are study-dependent and show no overall consistent pattern. Further improving the absolute accuracy of IWV measurements and providing climate-quality time series therefore remain challenging problems.

Time series of total column abundances of hydrogen chloride (HCl), chlorine nitrate (ClONO2), and hydrogen fluoride (HF) were determined from ground-based Fourier transform infrared (FTIR) spectra recorded at 17 sites belonging to the Network for the Detection of Atmospheric Composition Change (NDACC) and located between 80.05° N and 77.82° S. By providing such a near-global overview on ground-based measurements of the two major stratospheric chlorine reservoir species, HCl and ClONO2, the present study is able to confirm the decrease of the atmospheric inorganic chlorine abundance during the last few years. This decrease is expected following the 1987 Montreal Protocol and its amendments and adjustments, where restrictions and a subsequent phase-out of the prominent anthropogenic chlorine source gases (solvents, chlorofluorocarbons) were agreed upon to enable a stabilisation and recovery of the stratospheric ozone layer. The atmospheric fluorine content is expected to be influenced by the Montreal Protocol, too, because most of the banned anthropogenic gases also represent important fluorine sources. But many of the substitutes to the banned gases also contain fluorine so that the HF total column abundance is expected to have continued to increase during the last few years. The measurements are compared with calculations from five different models: the two-dimensional Bremen model, the two chemistry-transport models KASIMA and SLIMCAT, and the two chemistry-climate models EMAC and SOCOL. Thereby, the ability of the models to reproduce the absolute total column amounts, the seasonal cycles, and the temporal evolution found in the FTIR measurements is investigated and inter-compared. This is especially interesting because the models have different architectures. The overall agreement between the measurements and models for the total column abundances and the seasonal cycles is good. Linear trends of HCl, ClONO2, and HF are calculated from both measurement and model time series data, with a focus on the time range 2000–2009. This period is chosen because from most of the measurement sites taking part in this study, data are available during these years. The precision of the trends is estimated with the bootstrap resampling method. The sensitivity of the trend results with respect to the fitting function, the time of year chosen and time series length is investigated, as well as a bias due to the irregular sampling of the measurements. The measurements and model results investigated here agree qualitatively on a decrease of the chlorine species by around 1% yr−1. The models simulate an increase of HF of around 1% yr−1. This also agrees well with most of the measurements, but some of the FTIR series in the Northern Hemisphere show a stabilisation or even a decrease in the last few years. In general, for all three gases, the measured trends vary more strongly with latitude and hemisphere than the modelled trends. Relative to the FTIR measurements, the models tend to underestimate the decreasing chlorine trends and to overestimate the fluorine increase in the Northern Hemisphere. At most sites, the models simulate a stronger decrease of ClONO2 than of HCl. In the FTIR measurements, this difference between the trends of HCl and ClONO2 depends strongly on latitude, especially in the Northern Hemisphere.

This study compares CO in the Arctic stratosphere and mesosphere measured by ground-based microwave radiometry with simulations made with the Whole Atmosphere Community Climate Model driven with specified dynamical fields (SD-WACCM4) for the Arctic winters 2008/2009 and 2009/2010. CO is a tracer for polar winter middle atmosphere dynamics, hence the representation of polar dynamics in the model is examined indirectly. Measurements were taken with the KIruna Microwave RAdiometer (KIMRA). The instrument, which is located in Kiruna, Northern Sweden (67.8° N, 20.4° E), provides CO profiles between 40 and 80 km altitude. The present comparison, which is one of the first between SD-WACCM4 and measurements, is performed on the smallest space and time scales currently simulated by the model; the global model is evaluated daily at the particular model grid-point closest to Kiruna. As a guide to what can generally be expected from such a comparison, the same analysis is repeated for observations of CO from the Microwave Limb Sounder (MLS), a microwave radiometer onboard NASA's Aura satellite, which has global coverage. First, time-mean profiles of CO are compared, revealing that the profile shape of KIMRA deviates from SD-WACCM4 and MLS, especially in the upper mesosphere. SD-WACCM4 and MLS are mostly consistent throughout the range of altitude considered; however, SD-WACCM4 shows slightly lower values in the upper mesosphere. Second, the time evolution is compared for the complete time series, as well as for the slowly and rapidly evolving parts alone. Overall, the agreement among the datasets is very good and the model is almost as consistent with the measurements as the measurements are with each other. Mutual correlation coefficients of the slowly varying part of the CO time series are ≥0.9 over a wide altitude range. This demonstrates that the polar winter middle atmosphere dynamics is very well represented in SD-WACCM4 and that the relaxation to analyzed meteorological fields below 50 km constrains the behavior of the simulation sufficiently, even at higher altitudes, such that the simulation above 50 km is close to the measurements. However, above 50 km, the model-measurement correlation for the rapidly varying part of the CO time series is lower (0.3) than the measurement-measurement correlation (0.6). This is attributed to the fact that the gravity wave parametrization in WACCM is based on a generic gravity wave spectrum and cannot be expected to capture the instantaneous behavior of the actual gravity wave field present in the atmosphere.

CO serves as a tracer for dynamics in the polar winter middle atmosphere. This work presents the retrieval and the characterization of ground-based CO measurements from the winters 2008/2009 and 2009/2010 by the Kiruna microwave radiometer KIMRA, located in northern Sweden (67.8° N, 20.4° E). Furthermore, the dataset is used for an extensive comparison to the recent satellite instruments MLS on Aura, ACE-FTS, and MIPAS on Envisat. The vmr profiles are retrieved using the optimal estimation approach. A detailed analysis of the averaging kernel functions is carried out, showing sensitivity of the measurements between 40 and 80 km altitude, a vertical resolution of 16 to 22 km, as well as a residual influence of the region up to 130 km altitude. An error assessment reveals a total error of the retrieved profile that increases with altitude and is approx. ±0.1 ppmv at 50 km altitude and ±3 ppmv at 80 km altitude. The main contributions to this total error arise from the measurement noise and the uncertainty of the used temperature profiles. The expected dynamical features of the polar winter middle atmosphere are qualitatively identified in the retrieved time series, but are not quantitatively analyzed here. The dense MLS dataset is used to investigate the influence of the collocation criteria on the satellite comparison, showing that relaxing the distance criterion causes a high bias for MLS. The comparison including the other instruments is difficult because of the small number of coincidences. However, it suggests that there is a general agreement between KIMRA and the satellite instruments below 65 km altitude, but a high bias for KIMRA above this altitude. Furthermore, the shape of the KIMRA profile appears to be systematically different from the satellite profiles.

Trends in the CO andC2H6 partial columns ~0–15 km) have been estimated from four European ground-based solar FTIR (Fourier Transform InfraRed) stations for the 1996–2006 time period. The CO trends from the four stations Jungfraujoch, Zugspitze, Harestua and Kiruna have been estimated to −0.45 ± 0.16% yr−1, −1.00 ± 0.24% yr−1, −0.62 ± 0.19 % yr−1 and −0.61 ± 0.16% yr−1, respectively. The corresponding trends for C2H6 are −1.51 ± 0.23% yr−1, −2.11 ± 0.30% yr−1, −1.09 ± 0.25% yr−1 and −1.14 ± 0.18% yr−1. All trends are presented with their 2-σ confidence intervals. To find possible reasons for the CO trends, the global-scale EMEP MSC-W chemical transport model has been used in a series of sensitivity scenarios. It is shown that the trends are consistent with the combination of a 20% decrease in the anthropogenic CO emissions seen in Europe and North America during the 1996–2006 period and a 20% increase in the anthropogenic CO emissions in East Asia, during the same time period. The possible impacts of CH4 and biogenic volatile organic compounds (BVOCs) are also considered. The European and global-scale EMEP models have been evaluated against the measured CO and C2H6 partial columns from Jungfraujoch, Zugspitze, Bremen, Harestua, Kiruna and Ny-Ålesund. The European model reproduces, on average the measurements at the different sites fairly well and within 10–22% deviation for CO and 14–31% deviation for C2H6. Their seasonal amplitude is captured within 6–35% and 9–124% for CO and C2H6, respectively. However, 61–98% of the CO and C2H6 partial columns in the European model are shown to arise from the boundary conditions, making the global-scale model a more suitable alternative when modeling these two species. In the evaluation of the global model the average partial columns for 2006 are shown to be within 1–9% and 37–50% of the measurements for CO and C2H6, respectively. The global model sensitivity for assumptions made in this paper is also analyzed.

Trends of hydrogen chloride (HCl), chlorine nitrate (ClONO2), and hydrogen fluoride (HF) total column abundances above Kiruna (Northern Sweden, 67.84° N, 20.41° E) derived from nearly 14 years (1996–2009) of measurement and model data are presented. The measurements have been performed with a Bruker 120 HR (later Bruker 125 HR) Fourier transform infrared (FTIR) spectrometer and the chemistry-transport model (CTM) used was KASIMA (KArlsruhe SImulation model of the Middle Atmosphere). The total column abundances of ClONO2 and HF calculated by KASIMA agree quite well with the FTIR measurements while KASIMA tends to underestimate the HCl columns. To calculate the long-term trends, a linear function combined with an annual cycle was fitted to the data using a least squares method. The precision of the resulting trends was estimated with the bootstrap resampling method. For HF, both model and measurements show a positive trend that seems to decrease in the last few years. This suggests a stabilisation of the HF total column abundance. Between 1996 and 2009, KASIMA simulates an increase of (+1.51±0.07) %/yr which exceeds the FTIR result of (+0.65±0.25) %/yr. The trends determined for HCl and ClONO2 are significantly negative over the time period considered here. This is expected because the emission of their precursors (chlorofluorocarbons and hydrochlorofluorocarbons) has been restricted in the Montreal Protocol in 1987 and its amendments and adjustments. The trend for ClONO2 from the FTIR measurements amounts to (−3.28±0.56) %/yr and the one for HCl to (−0.81±0.23) %/yr. KASIMA simulates a weaker decrease: For ClONO2, the result is (−0.90±0.10) %/yr and for HCl (−0.17±0.06) %/yr. Part of the difference between measurement and model data can be explained by sampling and the stronger annual cycle indicated by the measurements. There is a factor of about four between the trends of HCl and ClONO2 above Kiruna for both measurement and model data.

This paper characterizes vertical ozone profiles retrieved with the IMK-IAA (Institute for Meteorology and Climate Research, Karlsruhe – Instituto de Astrofisica de Andalucia) science-oriented processor from high spectral resolution data (until March 2004) measured by the Michelson Interferometer for Passive Atmospheric Sounding (MIPAS) aboard the environmental satellite Envisat. Bias determination and precision validation is performed on the basis of correlative measurements by ground-based lidars, Fourier transform infrared spectrometers, and microwave radiometers as well as balloon-borne ozonesondes, the balloon-borne version of MIPAS, and two satellite instruments (Halogen Occultation Experiment and Polar Ozone and Aerosol Measurement III). Percentage mean differences between MIPAS and the comparison instruments for stratospheric ozone are generally within ±10%. The precision in this altitude region is estimated at values between 5 and 10% which gives an accuracy of 15 to 20%. Below 18 km, the spread of the percentage mean differences is larger and the precision degrades to values of more than 20% depending on altitude and latitude. The main reason for the degraded precision at low altitudes is attributed to undetected thin clouds which affect MIPAS retrievals, and to the influence of uncertainties in the water vapor concentration.

During the Arctic winter of 2000/01, ground-based FTIR and millimetre-wave measurements revealed significant amounts of ClO over Kiruna after the final warming in February 2001. In fact, column amounts of ClO were still increased in March 2001 when temperatures were about 20K above the PSC (Polar Stratospheric Clouds) threshold. At these temperatures, chlorine activation due to heterogeneous processes on PSCs is not possible even in the presence of strong lee wave effects. In order to discuss possible reasons of this feature, time series of other chemical species will be presented and discussed, too. Measurements of HF and COF2 indicated that vortex air was still observed in mid-March 2001. Since the time series of HNO3 column amounts do not give any evidence of a denitrification later than 11 February, chlorine activation persisting for several weeks after the presence of PSCs due to denitrification is rather unlikely. The photolysis of ClONO2-rich air which had been formed at the end of February and beginning of March 2001 as well as chlorine activation due to the presence of an unusual aerosol layer are discussed as possible causes of the increased ClO column amounts after the final warming.

We present ozone measurements from the millimetre wave radiometer installed at the Swedish Institute of Space Physics (Institutet för rymdfysik, IRF) in Kiruna (67.8° N, 20.4° E, 420 m asl). Nearly continuous operation in the winter of 2002/2003 allows us to give an overview of ozone evolution in the stratosphere between 15 and 55 km. In this study we present a detailed analysis of the Arctic winter 2002/2003. By means of a methodology using equivalent latitudes we investigate the meteorological processes in the stratosphere during the entire winter/spring period. During the course of the winter strong mixing into the vortex took place in the middle and upper stratosphere as a result of three minor and one major warming event, but no evidence was found for significant mixing in the lower stratosphere. Ozone depletion in the lower stratosphere during this winter was estimated by measurements on those days when Kiruna was well inside the Arctic polar vortex. The days were carefully chosen using a definition of the vortex edge based on equivalent latitudes. At the 475 K isentropic level a cumulative ozone loss of about 0.5 ppmv was found starting in January and lasting until mid-March. The early ozone loss is probably a result of the very cold temperatures in the lower stratosphere in December and the geographical extension of the vortex to lower latitudes where solar irradiation started photochemical ozone loss in the pre-processed air. In order to correct for dynamic effects of the ozone variation due to diabatic subsidence of air masses inside the vortex, we used N2O measurements from the Odin satellite for the same time period. The derived ozone loss in the lower stratosphere between mid-December and mid-March varies between 1.1±0.1 ppmv on the 150 ppbv N2O isopleth and 1.7±0.1 ppmv on the 50 ppbv N2O isopleth.