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  • 1
    In: Atmospheric Measurement Techniques, Copernicus GmbH, Vol. 14, No. 1 ( 2021-01-04), p. 1-35
    Abstract: Abstract. The second Cabauw Intercomparison of Nitrogen Dioxide measuring Instruments (CINDI-2) took place in Cabauw (the Netherlands) in September 2016 with the aim of assessing the consistency of multi-axis differential optical absorption spectroscopy (MAX-DOAS) measurements of tropospheric species (NO2, HCHO, O3, HONO, CHOCHO and O4). This was achieved through the coordinated operation of 36 spectrometers operated by 24 groups from all over the world, together with a wide range of supporting reference observations (in situ analysers, balloon sondes, lidars, long-path DOAS, direct-sun DOAS, Sun photometer and meteorological instruments). In the presented study, the retrieved CINDI-2 MAX-DOAS trace gas (NO2, HCHO) and aerosol vertical profiles of 15 participating groups using different inversion algorithms are compared and validated against the colocated supporting observations, with the focus on aerosol optical thicknesses (AOTs), trace gas vertical column densities (VCDs) and trace gas surface concentrations. The algorithms are based on three different techniques: six use the optimal estimation method, two use a parameterized approach and one algorithm relies on simplified radiative transport assumptions and analytical calculations. To assess the agreement among the inversion algorithms independent of inconsistencies in the trace gas slant column density acquisition, participants applied their inversion to a common set of slant columns. Further, important settings like the retrieval grid, profiles of O3, temperature and pressure as well as aerosol optical properties and a priori assumptions (for optimal estimation algorithms) have been prescribed to reduce possible sources of discrepancies. The profiling results were found to be in good qualitative agreement: most participants obtained the same features in the retrieved vertical trace gas and aerosol distributions; however, these are sometimes at different altitudes and of different magnitudes. Under clear-sky conditions, the root-mean-square differences (RMSDs) among the results of individual participants are in the range of 0.01–0.1 for AOTs, (1.5–15) ×1014molec.cm-2 for trace gas (NO2, HCHO) VCDs and (0.3–8)×1010molec.cm-3 for trace gas surface concentrations. These values compare to approximate average optical thicknesses of 0.3, trace gas vertical columns of 90×1014molec.cm-2 and trace gas surface concentrations of 11×1010molec.cm-3 observed over the campaign period. The discrepancies originate from differences in the applied techniques, the exact implementation of the algorithms and the user-defined settings that were not prescribed. For the comparison against supporting observations, the RMSDs increase to a range of 0.02–0.2 against AOTs from the Sun photometer, (11–55)×1014molec.cm-2 against trace gas VCDs from direct-sun DOAS observations and (0.8–9)×1010molec.cm-3 against surface concentrations from the long-path DOAS instrument. This increase in RMSDs is most likely caused by uncertainties in the supporting data, spatiotemporal mismatch among the observations and simplified assumptions particularly on aerosol optical properties made for the MAX-DOAS retrieval. As a side investigation, the comparison was repeated with the participants retrieving profiles from their own differential slant column densities (dSCDs) acquired during the campaign. In this case, the consistency among the participants degrades by about 30 % for AOTs, by 180 % (40 %) for HCHO (NO2) VCDs and by 90 % (20 %) for HCHO (NO2) surface concentrations. In former publications and also during this comparison study, it was found that MAX-DOAS vertically integrated aerosol extinction coefficient profiles systematically underestimate the AOT observed by the Sun photometer. For the first time, it is quantitatively shown that for optimal estimation algorithms this can be largely explained and compensated by considering biases arising from the reduced sensitivity of MAX-DOAS observations to higher altitudes and associated a priori assumptions.
    Type of Medium: Online Resource
    ISSN: 1867-8548
    Language: English
    Publisher: Copernicus GmbH
    Publication Date: 2021
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  • 2
    In: Atmospheric Chemistry and Physics, Copernicus GmbH, Vol. 23, No. 12 ( 2023-06-28), p. 7121-7139
    Abstract: Abstract. Heatwaves are a substantial health threat in the UK, exacerbated by co-occurrence of ozone pollution episodes. Here we report on the first use of retrieved vertical profiles of nitrogen dioxide (NO2) and formaldehyde (HCHO) over Central London from a newly installed multi-axis differential optical absorption spectroscopy (MAX-DOAS) instrument coincident with two of three heatwaves for the hottest summer on record. We evaluate space-based sensor observations routinely used to quantify temporal changes in air pollution and precursor emissions over London. Collocated daily mean tropospheric column densities from the high-spatial-resolution space-based TROPOspheric Monitoring Instrument (TROPOMI) and MAX-DOAS, after accounting for differences in vertical sensitivities, are temporally consistent for NO2 and HCHO (both R = 0.71). TROPOMI NO2 is 27 %–31 % less than MAX-DOAS NO2, as expected from horizontal dilution of NO2 by TROPOMI pixels in polluted cities. TROPOMI HCHO is 20 % more than MAX-DOAS HCHO, greater than differences in past validation studies but within the range of systematic errors in the MAX-DOAS retrieval. The MAX-DOAS near-surface (0–110 m) retrievals have similar day-to-day and hourly variability to the surface sites for comparison of NO2 (R ≥ 0.7) and for MAX-DOAS HCHO versus surface site isoprene (R ≥ 0.7) that oxidises to HCHO in prompt and high yields. Daytime ozone production, diagnosed with MAX-DOAS HCHO-to-NO2 tropospheric vertical column ratios, is mostly limited by availability of volatile organic compounds (VOCs), except on heatwave days. Temperature-dependent biogenic VOC emissions of isoprene increase exponentially, resulting in ozone concentrations that exceed the regulatory standard for ozone and cause non-compliance at urban background sites in Central London. Locations in Central London heavily influenced by traffic remain in compliance, but this is likely to change with stricter controls on vehicle emissions of NOx and higher likelihood of heatwave frequency, severity, and persistence due to anthropogenic climate change.
    Type of Medium: Online Resource
    ISSN: 1680-7324
    Language: English
    Publisher: Copernicus GmbH
    Publication Date: 2023
    detail.hit.zdb_id: 2092549-9
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  • 3
    In: Atmospheric Chemistry and Physics, Copernicus GmbH, Vol. 21, No. 5 ( 2021-03-04), p. 3371-3393
    Abstract: Abstract. Volcanic emissions are a source of halogens in the atmosphere. Rapid reactions convert the initially emitted hydrogen halides (HCl, HBr, and HI) into reactive species such as BrO, Br2, BrCl, ClO, OClO, and IO. The activation reaction mechanisms in the plume consume ozone (O3), which is entrained by ambient air that is mixed into the plume. In this study, we present observations of the oxidation of bromine, chlorine, and iodine during the first 11 min following emission, examining the plume from Santiago crater of the Masaya volcano in Nicaragua. Two field campaigns were conducted: one in July 2016 and one in September 2016. The sum of the reactive species of each halogen was determined by gas diffusion denuder sampling followed by gas chromatography–mass spectrometry (GC-MS) analysis, whereas the total halogens and sulfur concentrations were obtained by alkaline trap sampling with subsequent ion chromatography (IC) and inductively coupled plasma mass spectrometry (ICP-MS) measurements. Both ground and airborne sampling with an unoccupied aerial vehicle (carrying a denuder sampler in combination with an electrochemical SO2 sensor) were conducted at varying distances from the crater rim. The in situ measurements were accompanied by remote sensing observations (differential optical absorption spectroscopy; DOAS). The reactive fraction of bromine increased from 0.20 ± 0.13 at the crater rim to 0.76 ± 0.26 at 2.8 km downwind, whereas chlorine showed an increase in the reactive fraction from (2.7 ± 0.7) × 10−4 to (11 ± 3) × 10−4 in the first 750 m. Additionally, a reactive iodine fraction of 0.3 at the crater rim and 0.9 at 2.8 km downwind was measured. No significant change in BrO / SO2 molar ratios was observed with the estimated age of the observed plume ranging from 1.4 to 11.1 min. This study presents a large complementary data set of different halogen compounds at Masaya volcano that allowed for the quantification of reactive bromine in the plume of Masaya volcano at different plume ages. With the observed field data, a chemistry box model (Chemistry As A Boxmodel Application Module Efficiently Calculating the Chemistry of the Atmosphere; CAABA/MECCA) allowed us to reproduce the observed trend in the ratio of the reactive bromine to total bromine ratio. An observed contribution of BrO to the reactive bromine fraction of about 10 % was reproduced in the first few minutes of the model run.
    Type of Medium: Online Resource
    ISSN: 1680-7324
    Language: English
    Publisher: Copernicus GmbH
    Publication Date: 2021
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  • 4
    In: Atmospheric Measurement Techniques, Copernicus GmbH, Vol. 13, No. 2 ( 2020-02-13), p. 685-712
    Abstract: Abstract. 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.
    Type of Medium: Online Resource
    ISSN: 1867-8548
    Language: English
    Publisher: Copernicus GmbH
    Publication Date: 2020
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  • 5
    In: Atmospheric Measurement Techniques, Copernicus GmbH, Vol. 13, No. 5 ( 2020-05-06), p. 2169-2208
    Abstract: Abstract. 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.
    Type of Medium: Online Resource
    ISSN: 1867-8548
    Language: English
    Publisher: Copernicus GmbH
    Publication Date: 2020
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  • 6
    In: Atmospheric Measurement Techniques, Copernicus GmbH, Vol. 13, No. 9 ( 2020-09-29), p. 5087-5116
    Abstract: Abstract. 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.
    Type of Medium: Online Resource
    ISSN: 1867-8548
    Language: English
    Publisher: Copernicus GmbH
    Publication Date: 2020
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  • 7
    Online Resource
    Online Resource
    Copernicus GmbH ; 2022
    In:  Atmospheric Measurement Techniques Vol. 15, No. 7 ( 2022-04-05), p. 2077-2098
    In: Atmospheric Measurement Techniques, Copernicus GmbH, Vol. 15, No. 7 ( 2022-04-05), p. 2077-2098
    Abstract: Abstract. Ground-based multi-axis differential optical absorption spectroscopy (MAX-DOAS) is a widely used measurement technique for the remote detection of atmospheric aerosol and trace gases. The technique relies on the analysis of ultra-violet and visible radiation spectra of scattered sunlight (skylight) to obtain information on different atmospheric parameters. From an appropriate set of spectra recorded under different viewing directions (typically a group of observations at different elevation angles) the retrieval of aerosol and trace gas vertical distributions is achieved through numerical inversion methods. It is well known that the polarisation state of skylight is particularly sensitive to atmospheric aerosol content as well as aerosol properties and that polarimetric measurements could therefore provide additional information for MAX-DOAS profile retrievals; however, such measurements have not yet been used for this purpose. To address this issue, we have developed the RAPSODI (Retrieval of Atmospheric Parameters from Spectroscopic Observations using DOAS Instruments) algorithm. In contrast to existing MAX-DOAS algorithms, it can process polarimetric information, and it can retrieve simultaneously profiles of aerosols and various trace gases at multiple wavelengths in a single retrieval step; a further advantage is that it contains a Mie scattering model, allowing for the retrieval of aerosol microphysical properties. The forward-model component in RAPSODI is based on a linearised vector radiative transfer model with Jacobian facilities, and we have used this model to create a database of synthetic measurements in order to carry out sensitivity analyses aimed at assessing the potential of polarimetric MAX-DOAS observations. We find that multispectral polarimetry significantly enhances the sensitivity, particularly to aerosol-related quantities. Assuming typical viewing geometries, the degrees of freedom for signal (DOFS) increase by about 50 % and 70 % for aerosol vertical distributions and aerosol properties, respectively, and by approximately 10 % for trace gas vertical profiles. For an idealised scenario with a horizontally homogeneous atmosphere, our findings predict an improvement in the inversion results' accuracy (root-mean-square deviations to the true values) of about 60 % for aerosol vertical column densities (VCDs) as well as for aerosol surface concentrations and by 40 % for aerosol properties. For trace gas VCDs, very little improvement is apparent, although the accuracy of trace gas surface concentrations improves by about 50 %.
    Type of Medium: Online Resource
    ISSN: 1867-8548
    Language: English
    Publisher: Copernicus GmbH
    Publication Date: 2022
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  • 8
    In: Atmospheric Measurement Techniques, Copernicus GmbH, Vol. 11, No. 4 ( 2018-04-26), p. 2441-2457
    Abstract: Abstract. 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.
    Type of Medium: Online Resource
    ISSN: 1867-8548
    Language: English
    Publisher: Copernicus GmbH
    Publication Date: 2018
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  • 9
    In: Atmospheric Measurement Techniques, Copernicus GmbH, Vol. 12, No. 4 ( 2019-04-10), p. 2155-2181
    Abstract: Abstract. 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.
    Type of Medium: Online Resource
    ISSN: 1867-8548
    Language: English
    Publisher: Copernicus GmbH
    Publication Date: 2019
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  • 10
    In: EPJ Web of Conferences, EDP Sciences, Vol. 176 ( 2018), p. 10005-
    Abstract: For the validation of space borne observations of NO2 and other trace gases from hyperspectral imagers, ground based instruments based on the MAXDOAS technique are an excellent choice, since they rely on similar retrieval techniques as the observations from orbit. To ensure proper traceability of the MAXDOAS observations, a thorough validation and intercomparison is mandatory. Advanced MAXDOAS observation and retrieval techniques enable inferring vertical structure of trace gases and aerosols. These techniques and their results need validation by e.g. lidar techniques. For the proper understanding of the results from passive remote sensing techniques, independent observations are needed that include parameters needed to understand the light paths, i.e. in-situ aerosol observations of optical and microphysical properties, and essential are in particular the vertical profiles of aerosol optical properties by (Raman) lidar. The approach used in the CINDI-2 campaign held in Cabauw in 2016 is presented in this paper and the results will be discussed in the presentation at the conference.
    Type of Medium: Online Resource
    ISSN: 2100-014X
    Language: English
    Publisher: EDP Sciences
    Publication Date: 2018
    detail.hit.zdb_id: 2595425-8
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