ALBERT

Description: In September 2016, 36 spectrometers from 24 institutes measured a number of key atmospheric pollutants for a period of 17 d during the Second Cabauw Intercomparison campaign for Nitrogen Dioxide measuring Instruments (CINDI-2) that took place at Cabauw, the Netherlands (51.97∘ N, 4.93∘ E). We report on the outcome of the formal semi-blind intercomparison exercise, which was held under the umbrella of the Network for the Detection of Atmospheric Composition Change (NDACC) and the European Space Agency (ESA). The three major goals of CINDI-2 were (1) to characterise and better understand the differences between a large number of multi-axis differential optical absorption spectroscopy (MAX-DOAS) and zenith-sky DOAS instruments and analysis methods, (2) to define a robust methodology for performance assessment of all participating instruments, and (3) to contribute to a harmonisation of the measurement settings and retrieval methods. This, in turn, creates the capability to produce consistent high-quality ground-based data sets, which are an essential requirement to generate reliable long-term measurement time series suitable for trend analysis and satellite data validation. The data products investigated during the semi-blind intercomparison are slant columns of nitrogen dioxide (NO2), the oxygen collision complex (O4) and ozone (O3) measured in the UV and visible wavelength region, formaldehyde (HCHO) in the UV spectral region, and NO2 in an additional (smaller) wavelength range in the visible region. The campaign design and implementation processes are discussed in detail including the measurement protocol, calibration procedures and slant column retrieval settings. Strong emphasis was put on the careful alignment and synchronisation of the measurement systems, resulting in a unique set of measurements made under highly comparable air mass conditions. The CINDI-2 data sets were investigated using a regression analysis of the slant columns measured by each instrument and for each of the target data products. The slope and intercept of the regression analysis respectively quantify the mean systematic bias and offset of the individual data sets against the selected reference (which is obtained from the median of either all data sets or a subset), and the rms error provides an estimate of the measurement noise or dispersion. These three criteria are examined and for each of the parameters and each of the data products, performance thresholds are set and applied to all the measurements. The approach presented here has been developed based on heritage from previous intercomparison exercises. It introduces a quantitative assessment of the consistency between all the participating instruments for the MAX-DOAS and zenith-sky DOAS techniques.

Description: We present the inter-comparison of delta slant column densities (SCDs) and vertical profiles of nitrous acid (HONO) derived from measurements of different multi-axis differential optical absorption spectroscopy (MAX-DOAS) instruments and using different inversion algorithms during the Second Cabauw Inter-comparison campaign for Nitrogen Dioxide measuring Instruments (CINDI-2) in September 2016 at Cabauw, the Netherlands (51.97∘ N, 4.93∘ E). The HONO vertical profiles, vertical column densities (VCDs), and near-surface volume mixing ratios are compared between different MAX-DOAS instruments and profile inversion algorithms for the first time. Systematic and random discrepancies of the HONO results are derived from the comparisons of all data sets against their median values. Systematic discrepancies of HONO delta SCDs are observed in the range of ±0.3×1015 molec. cm−2, which is half of the typical random discrepancy of 0.6×1015 molec. cm−2. For a typical high HONO delta SCD of 2×1015 molec. cm−2, the relative systematic and random discrepancies are about 15 % and 30 %, respectively. The inter-comparison of HONO profiles shows that both systematic and random discrepancies of HONO VCDs and near-surface volume mixing ratios (VMRs) are mostly in the range of ∼±0.5×1014 molec. cm−2 and ∼±0.1 ppb (typically ∼20 %). Further we find that the discrepancies of the retrieved HONO profiles are dominated by discrepancies of the HONO delta SCDs. The profile retrievals only contribute to the discrepancies of the HONO profiles by ∼5 %. However, some data sets with substantially larger discrepancies than the typical values indicate that inappropriate implementations of profile inversion algorithms and configurations of radiative transfer models in the profile retrievals can also be an important uncertainty source. In addition, estimations of measurement uncertainties of HONO dSCDs, which can significantly impact profile retrievals using the optimal estimation method, need to consider not only DOAS fit errors, but also atmospheric variability, especially for an instrument with a DOAS fit error lower than ∼3×1014 molec. cm−2. The MAX-DOAS results during the CINDI-2 campaign indicate that the peak HONO levels (e.g. near-surface VMRs of ∼0.4 ppb) often appeared in the early morning and below 0.2 km. The near-surface VMRs retrieved from the MAX-DOAS observations are compared with those measured using a co-located long-path DOAS instrument. The systematic differences are smaller than 0.15 and 0.07 ppb during early morning and around noon, respectively. Since true HONO values at high altitudes are not known in the absence of real measurements, in order to evaluate the abilities of profile inversion algorithms to respond to different HONO profile shapes, we performed sensitivity studies using synthetic HONO delta SCDs simulated by a radiative transfer model with assumed HONO profiles. The tests indicate that the profile inversion algorithms based on the optimal estimation method with proper configurations can reproduce the different HONO profile shapes well. Therefore we conclude that the features of HONO accumulated near the surface derived from MAX-DOAS measurements are expected to represent the ambient HONO profiles well.

Description: Multi-axis differential optical absorption spectroscopy (MAX-DOAS) is a widely used measurement technique for the detection of a variety of atmospheric trace gases. Using inverse modelling, the observation of trace gas column densities along different lines of sight enables the retrieval of aerosol and trace gas vertical profiles in the atmospheric boundary layer using appropriate retrieval algorithms. In this study, the ability of eight profile retrieval algorithms to reconstruct vertical profiles is assessed on the basis of synthetic measurements. Five of the algorithms are based on the optimal estimation method, two on parametrised approaches, and one using an analytical approach without involving any radiative transfer modelling. The synthetic measurements consist of the median of simulated slant column densities of O4 at 360 and 477 nm, as well as of HCHO at 343 nm and NO2 at 477 nm, from seven datasets simulated by five different radiative transfer models. Simulations are performed for a combination of 10 trace gas and 11 aerosol profiles, as well as 11 elevation angles, three solar zenith, and three relative azimuth angles. Overall, the results from the different algorithms show moderate to good performance for the retrieval of vertical profiles, surface concentrations, and total columns. Except for some outliers, the root-mean-square difference between the true and retrieved state ranges between (0.05–0.1) km−1 for aerosol extinction and (2.5–5.0) ×1010 molec cm−3 for HCHO and NO2 concentrations.

Description: Volcanoes are a natural source of several reactive gases (e.g., sulfur and halogen containing species) and nonreactive gases (e.g., carbon dioxide) to the atmosphere. The relative abundance of carbon and sulfur in volcanic gas as well as the total sulfur dioxide emission rate from a volcanic vent are established parameters in current volcano-monitoring strategies, and they oftentimes allow insights into subsurface processes. However, chemical reactions involving halogens are thought to have local to regional impact on the atmospheric chemistry around passively degassing volcanoes. In this study we demonstrate the successful deployment of a multirotor UAV (quadcopter) system with custom-made lightweight payloads for the compositional analysis and gas flux estimation of volcanic plumes. The various applications and their potential are presented and discussed in example studies at three volcanoes encompassing flight heights of 450 to 3300 m and various states of volcanic activity. Field applications were performed at Stromboli volcano (Italy), Turrialba volcano (Costa Rica) and Masaya volcano (Nicaragua). Two in situ gas-measuring systems adapted for autonomous airborne measurements, based on electrochemical and optical detection principles, as well as an airborne sampling unit, are introduced. We show volcanic gas composition results including abundances of CO2, SO2 and halogen species. The new instrumental setups were compared with established instruments during ground-based measurements at Masaya volcano, which resulted in CO2 ∕ SO2 ratios of 3.6 ± 0.4. For total SO2 flux estimations a small differential optical absorption spectroscopy (DOAS) system measured SO2 column amounts on transversal flights below the plume at Turrialba volcano, giving 1776 ± 1108 T d−1 and 1616 ± 1007 T d−1 of SO2 during two traverses. At Stromboli volcano, elevated CO2 ∕ SO2 ratios were observed at spatial and temporal proximity to explosions by airborne in situ measurements. Reactive bromine to sulfur ratios of 0.19 × 10−4 to 9.8 × 10−4 were measured in situ in the plume of Stromboli volcano, downwind of the vent.

Description: We present different methods for in-field elevation calibration of MAX-DOAS (Multi AXis Differential Optical Absorption Spectroscopy) instruments that were applied and inter-compared during the second Cabauw Intercomparison campaign for Nitrogen Dioxide measuring Instruments (CINDI-2). One necessary prerequisite of consistent MAX-DOAS retrievals is a precise and accurate calibration of the elevation angles of the different measuring systems. Therefore, different methods for this calibration were applied to several instruments during the campaign, and the results were inter-compared. This work first introduces and explains the different methods, namely far- and near-lamp measurements, white-stripe scans, horizon scans and sun scans, using data and results for only one (mainly the Max Planck Institute for Chemistry) instrument. In the second part, the far-lamp measurements and the horizon scans are examined for all participating groups. Here, the results for both methods are first inter-compared for the different instruments; secondly, the two methods are compared amongst each other. All methods turned out to be well-suited for the calibration of the elevation angles of MAX-DOAS systems, with each of them having individual advantages and drawbacks. Considering the results of this study, the systematic uncertainties of the methods can be estimated as ±0.05∘ for the far-lamp measurements and the sun scans, ±0.25∘ for the horizon scans, and around ±0.1∘ for the white-stripe and near-lamp measurements. When comparing the results of far-lamp and horizon-scan measurements, a spread of around 0.9∘ in the elevation calibrations is found between the participating instruments for both methods. This spread is of the order of a typical field of view (FOV) of a MAX-DOAS instrument and therefore affecting the retrieval results. Further, consistent (wavelength dependent) offsets of 0.32∘ and 0.40∘ between far-lamp measurements and horizon scans are found, which can be explained by the fact that, despite the flat topography around the measurement site, obstacles such as trees might mark the visible horizon during daytime. The observed wavelength dependence can be explained by surface albedo effects. Lastly, the results are discussed and recommendations for future campaigns are given.