ALBERT

Description: Three years of Multi-Axis Differential Optical Absorption Spectroscopy (MAXDOAS) measurements (2011–2013) have been used for estimating the NO2 mixing ratio along a horizontal line of sight from the high mountain Subtropical observatory of Izaña, at 2370 m a.s.l. (NDACC station, 28.3° N, 16.5° W). The method is based on horizontal path calculation from the O2–O2 collisional complex at the 477 nm absorption band which is measured simultaneously to the NO2, and is applicable under low aerosols loading conditions. The MAXDOAS technique, applied in horizontal mode in the free troposphere, minimizes the impact of the NO2 contamination resulting from the arrival of MBL airmasses from thermally forced upwelling breeze during central hours of the day. Comparisons with in-situ observations show that during most of measuring period the MAXDOAS is insensitive or very little sensitive to the upwelling breeze. Exceptions are found during pollution events under southern wind conditions. On these occasions, evidence of fast efficient and irreversible transport from the surface to the free troposphere is found. Background NO2 vmr, representative of the remote free troposphere, are in the range of 20–45 pptv. The observed seasonal evolution shows an annual wave where the peak is in phase with the solar radiation. Model simulations with the chemistry-climate CAM-Chem model are in good agreement with the NO2 measurements, and are used to further investigate the possible drivers of the NO2 seasonality observed at Izaña.

Description: 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.

Description: 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‰.

Description: Within the project MUSICA (MUlti-platform remote Sensing of Isotopologues for investigating the Cycle of Atmospheric water), long-term tropospheric water vapour isotopologue data records are provided for ten globally distributed ground-based mid-infrared remote sensing stations of the NDACC (Network for the Detection of Atmospheric Composition Change). We present a new method allowing for an extensive and straightforward characterisation of the complex nature of such isotopologue remote sensing datasets. We demonstrate that the MUSICA humidity profiles are representative for most of the troposphere with a vertical resolution ranging from about 2 km (in the lower troposphere) to 8 km (in the upper troposphere) and with an estimated precision of better than 10%. We find that the sensitivity with respect to the isotopologue composition is limited to the lower and middle troposphere, whereby we estimate a precision of about 30‰ for the ratio between the two isotopologues HD16O and H216O. The measurement noise, the applied atmospheric temperature profiles, the uncertainty in the spectral baseline, and the cross-dependence on humidity are the leading error sources. We introduce an a posteriori correction method of the cross-dependence on humidity, and we recommend applying it to isotopologue ratio remote sensing datasets in general. In addition, we present mid-infrared CO2 retrievals and use them for demonstrating the MUSICA network-wide data consistency. In order to indicate the potential of long-term isotopologue remote sensing data if provided with a well-documented quality, we present a climatology and compare it to simulations of an isotope incorporated AGCM (Atmospheric General Circulation Model). We identify differences in the multi-year mean and seasonal cycles that significantly exceed the estimated errors, thereby indicating deficits in the modeled atmospheric water cycle.

Description: This study examines the possibility of ground-based remote-sensing ozone total column amounts (OTC) from spectral signatures at 3040 and 4030 cm−1. These spectral regions are routinely measured by the NDACC (Network for the Detection of Atmospheric Composition Change) ground-based FTIR (Fourier transform infraRed) experiments. In addition, they are potentially detectable by the TCCON (Total Carbon Column Observing Network) FTIR instruments. The ozone retrieval strategy presented here estimates the OTC from NDACC FTIR high-resolution spectra with a theoretical precision of about 2 and 5% in the 3040 and 4030 cm−1 regions, respectively. Empirically, these OTC products are validated by inter-comparison to FTIR OTC reference retrievals in the 1000 cm−1 spectral region (standard reference for NDACC ozone products), using an 8-year FTIR time series (2005–2012) taken at the subtropical ozone supersite of the Izaña Atmospheric Observatory (Tenerife, Spain). Associated with the weaker ozone signatures at the higher wave number regions, the 3040 and 4030 cm−1 retrievals show lower vertical sensitivity than the 1000 cm−1 retrievals. Nevertheless, we observe that the rather consistent variations are detected: the variances of the 3040 cm−1 and the 4030 cm−1 retrievals agree within 90 and 75%, respectively, with the variance of the 1000 cm−1 standard retrieval. Furthermore, all three retrievals show very similar annual cycles. However, we observe a large systematic difference of about 7% between the OTC obtained at 1000 and 3040 cm−1, indicating a significant inconsistency between the spectroscopic ozone parameters (HITRAN, 2012) of both regions. Between the 1000 cm and the 4030 cm−1 retrieval the systematic difference is only 2–3%. Finally, the long-term stability of the OTC retrievals has also been examined, observing that both near-infrared retrievals can monitor the long-term OTC evolution, consistent with the 1000 cm−1 reference data. These findings demonstrate that recording the solar absorption spectra in the 3000 cm−1 spectral region at high spectral resolution (about 0.005 cm−1) might be useful for TCCON sites. Hence, both NDACC and TCCON ground-based FTIR experiments might contribute to global ozone databases.

Description: A new approximation is proposed to estimate O3 and NO2 mixing ratios in the northern subtropical free troposphere (FT). The proposed method uses O4 slant column densities (SCDs) at horizontal and near-zenith geometries to estimate a station-level differential path. The modified geometrical approach (MGA) is a simple method that takes advantage of a very long horizontal path to retrieve mixing ratios in the range of a few pptv. The methodology is presented, and the possible limitations are discussed. Multi-axis differential optical absorption spectroscopy (MAX-DOAS) high-mountain measurements recorded at the Izaña observatory (28° 18' N, 16° 29' W) are used in this study. The results show that under low aerosol loading, O3 and NO2 mixing ratios can be retrieved even at very low concentrations. The obtained mixing ratios are compared with those provided by in situ instrumentation at the observatory. The MGA reproduces the O3 mixing ratio measured by the in situ instrumentation with a difference of 28%. The different air masses scanned by each instrument are identified as a cause of the discrepancy between the O3 observed by MAX-DOAS and the in situ measurements. The NO2 is in the range of 20–40 ppt, which is below the detection limit of the in situ instrumentation, but it is in agreement with measurements from previous studies for similar conditions.

Description: The project MUSICA (MUlti-platform remote Sensing of Isotopologues for investigating the Cycle of Atmospheric water) integrates tropospheric water vapour isotopologue remote sensing and in situ observations. This paper presents a first empirical validation of MUSICA's H2O and δD remote sensing products, generated from ground-based FTIR (Fourier transform infrared), spectrometer and space-based IASI (infrared atmospheric sounding interferometer) observation. The study is made in the area of the Canary Islands in the subtropical northern Atlantic. As reference we use well calibrated in situ measurements made aboard an aircraft (between 200 and 6800 m a.s.l.) by the dedicated ISOWAT instrument and on the island of Tenerife at two different altitudes (at Izaña, 2370 m a.s.l., and at Teide, 3550 m a.s.l.) by two commercial Picarro L2120-i water isotopologue analysers. The comparison to the ISOWAT profile measurements shows that the remote sensors can well capture the variations in the water vapour isotopologues, and the scatter with respect to the in situ references suggests a δD random uncertainty for the FTIR product of much better than 45‰ in the lower troposphere and of about 15‰ for the middle troposphere. For the middle tropospheric IASI δD product the study suggests a respective uncertainty of about 15‰. In both remote sensing data sets we find a positive δD bias of 30–70‰. Complementing H2O observations with δD data allows moisture transport studies that are not possible with H2O observations alone. We are able to qualitatively demonstrate the added value of the MUSICA δD remote sensing data. We document that the δD–H2O curves obtained from the different in situ and remote sensing data sets (ISOWAT, Picarro at Izaña and Teide, FTIR, and IASI) consistently identify two different moisture transport pathways to the subtropical north eastern Atlantic free troposphere.

Description: This study investigates the long-term evolution of subtropical ozone profile time series (1999–2010) obtained from ground-based FTIR (Fourier Transform InfraRed) spectrometry at the Izaña Observatory ozone super-site. Different ozone retrieval strategies are examined, analysing the influence of an additional temperature retrieval and different constraints. The theoretical assessment reveals that the FTIR system is able to resolve four independent ozone layers with a precision of better than 6% in the troposphere and of better than 3% in the lower, middle and upper stratosphere. This total error includes the smoothing error, which dominates the random error budget. Furthermore, we estimate that the measurement noise as well as uncertainties in the applied atmospheric temperature profiles and instrumental line shape are leading error sources. We show that a simultaneous temperature retrieval can significantly reduce the total random errors and that a regular determination of the instrumental line shape is important for producing a consistent long-term dataset. These theoretical precision estimates are empirically confirmed by daily intercomparisons with Electro Chemical Cell (ECC) sonde profiles. In order to empirically document the long-term stability of the FTIR ozone profile data we compare the linear trends and seasonal cycles as obtained from the FTIR and ECC time series. Concerning seasonality, in winter both techniques observe stratospheric ozone profiles that are typical middle latitude profiles (low tropopause, low ozone maximum concentrations) and in summer/autumn profiles that are typical tropical profiles (high tropopause, high maximum concentrations). The linear trends estimated from the FTIR and the ECC datasets agree within their error bars. For the FTIR time series, we observe a significant negative trend in the upper troposphere/lower stratosphere of about −0.2% yr−1 and a significant positive trend in the middle and upper stratosphere of about +0.3% yr−1 and +0.4% yr−1, respectively. Identifying such small trends is a difficult task for any measurement technique. In this context, super-sites applying different techniques are very important for the detection of reliable ozone trends.

Description: We present lower/middle tropospheric column-averaged CH4 mole fraction time series measured by nine globally distributed ground-based FTIR (Fourier transform infrared) remote sensing experiments of the Network for the Detection of Atmospheric Composition Change (NDACC). We show that these data are well representative of the tropospheric regional-scale CH4 signal, largely independent of the local surface small-scale signals, and only weakly dependent on upper tropospheric/lower stratospheric (UTLS) CH4 variations. In order to achieve the weak dependency on the UTLS, we use an a posteriori correction method. We estimate a typical precision for daily mean values of about 0.5% and a systematic error of about 2.5%. The theoretical assessments are complemented by an extensive empirical study. For this purpose, we use surface in situ CH4 measurements made within the Global Atmosphere Watch (GAW) network and compare them to the remote sensing data. We briefly discuss different filter methods for removing the local small-scale signals from the surface in situ data sets in order to obtain the in situ regional-scale signals. We find good agreement between the filtered in situ and the remote sensing data. The agreement is consistent for a variety of timescales that are interesting for CH4 source/sink research: day-to-day, monthly, and inter-annual. The comparison study confirms our theoretical estimations and proves that the NDACC FTIR measurements can provide valuable data for investigating the cycle of CH4.

Description: Three years of multi-axis differential optical absorption spectroscopy (MAXDOAS) measurements (2011–2013) have been used for estimating the NO2 mixing ratio along a horizontal line of sight from the high mountain subtropical observatory of Izaña, at 2370 m a.s.l. (NDACC station, 28.3° N, 16.5° W). The method is based on horizontal path calculation from the O2–O2 collisional complex at the 477 nm absorption band which is measured simultaneously to the NO2 column density, and is applicable under low aerosol-loading conditions. The MAXDOAS technique, applied in horizontal mode in the free troposphere, minimizes the impact of the NO2 contamination resulting from the arrival of marine boundary layer (MBL) air masses from thermally forced upwelling breeze during middle hours of the day. Comparisons with in situ observations show that during most of the measuring period, the MAXDOAS is insensitive or very slightly sensitive to the upwelling breeze. Exceptions are found for pollution events during southern wind conditions. On these occasions, evidence of fast, efficient and irreversible transport from the surface to the free troposphere is found. Background NO2 volume mixing ratio (vmr), representative of the remote free troposphere, is in the range of 20–45 pptv. The observed seasonal evolution shows an annual wave where the peak is in phase with the solar radiation. Model simulations with the chemistry–climate CAM-Chem model are in good agreement with the NO2 measurements, and are used to further investigate the possible drivers of the NO2 seasonality observed at Izaña.