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: Mt. Waliguan Observatory (WLG) is a World Meteorological Organization (WMO) Global Atmosphere Watch (GAW) global baseline station in China. WLG is located at the northeastern part of the Tibetan Plateau (36∘17′ N, 100∘54′ E, 3816 m a.s.l.) and is representative of the pristine atmosphere over the Eurasian continent. We made long-term ground-based multi-axis differential optical absorption spectroscopy (MAX-DOAS) measurements at WLG during the period 2012–2015. In this study, we retrieve the differential slant column densities (dSCDs) and estimate the tropospheric background mixing ratios of different trace gases, including NO2, SO2, HCHO, and BrO, using the measured spectra at WLG. Averaging of 10 original spectra is found to be an “optimum option” for reducing both the statistical error of the spectral retrieval and systematic errors in the analysis. The dSCDs of NO2, SO2, HCHO, and BrO under clear-sky and low-aerosol-load conditions are extracted from measured spectra at different elevation angles at WLG. By performing radiative transfer simulations with the model TRACY-2, we establish approximate relationships between the trace gas dSCDs at 1∘ elevation angle and the corresponding average tropospheric background volume mixing ratios. Mixing ratios of these trace gases in the lower troposphere over WLG are estimated to be in a range of about 7 ppt (January) to 100 ppt (May) for NO2, below 0.5 ppb for SO2, between 0.4 and 0.9 ppb for HCHO, and lower than 0.3 ppt for BrO. The chemical box model simulations constrained by the NO2 concentration from our MAX-DOAS measurements show that there is a little net ozone loss (−0.8 ppb d−1) for the free-tropospheric conditions and a little net ozone production (0.3 ppb d−1) for the boundary layer conditions over WLG during summertime. Our study provides valuable information and data sets for further investigating tropospheric chemistry in the background atmosphere and its links to anthropogenic activities.

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: The instrumental spectral response function (ISRF) is a key quantity in DOAS analysis, as it is needed for wavelength calibration and for the convolution of trace gas cross sections to instrumental resolution. While it can generally be measured using monochromatic stimuli, it is often parameterized in order to merge different calibration measurements and to plainly account for its wavelength dependency. For some instruments, the ISRF can be described appropriately by a Gaussian function, while for others, dedicated, complex parameterizations with several parameters have been developed.Here we propose to parameterize the ISRF as a super-Gaussian, which can reproduce a variety of shapes, from point-hat to boxcar shape, by just adding one parameter to the classical Gaussian. The super-Gaussian turned out to describe the ISRF of various DOAS instruments well, including the satellite instruments GOME-2, OMI, and TROPOMI.In addition, the super-Gaussian allows for a straightforward parameterization of the effect of ISRF changes, which can occur on long-term scales as well as, for example, during one satellite orbit and impair the spectral analysis if ignored. In order to account for such changes, spectral structures are derived from the derivatives of the super-Gaussian, which are afterwards just scaled during spectral calibration or DOAS analysis. This approach significantly improves the fit quality compared to setups with fixed ISRF, without drawbacks on computation time due to the applied linearization. In addition, the wavelength dependency of the ISRF can be accounted for by accordingly derived spectral structures in an easy, fast, and robust way.

Description: Experience of differential atmospheric absorption spectroscopy (DOAS) shows that a spectral shift between measurement spectra and reference spectra is frequently required in order to achieve optimal fit results, while the straightforward calculation of the optical density proves inferior. The shift is often attributed to temporal instabilities of the instrument but implicitly solved the problem of the tilt effect discussed/explained in this paper. Spectral positions of Fraunhofer and molecular absorption lines are systematically shifted for different measurement geometries due to an overall slope – or tilt – of the intensity spectrum. The phenomenon has become known as the tilt effect for limb satellite observations, where it is corrected for in a first-order approximation, whereas the remaining community is less aware of its cause and consequences. It is caused by the measurement process, because atmospheric absorption and convolution in the spectrometer do not commute. Highly resolved spectral structures in the spectrum will first be modified by absorption and scattering processes in the atmosphere before they are recorded with a spectrometer, which convolves them with a specific instrument function. In the DOAS spectral evaluation process, however, the polynomial (or other function used for this purpose) accounting for broadband absorption is applied after the convolution is performed. In this paper, we derive that changing the order of the two modifications of the spectra leads to different results. Assuming typical geometries for the observations of scattered sunlight and a spectral resolution of 0.6 nm, this effect can be interpreted as a spectral shift of up to 1.5 pm, which is confirmed in the actual analysis of the ground-based measurements of scattered sunlight as well as in numerical radiative transfer simulations. If no spectral shift is allowed by the fitting routine, residual structures of up to 2.5 × 10−3 peak-to-peak are observed. Thus, this effect needs to be considered for DOAS applications aiming at an rms of the residual of 10−3 and below.

Description: Knowledge of the field of view (FOV) of a remote sensing instrument is particularly important when interpreting their data and merging them with other spatially referenced data. Especially for instruments in space, information on the actual FOV, which may change during operation, may be difficult to obtain. Also, the FOV of ground-based devices may change during transportation to the field site, where appropriate equipment for the FOV determination may be unavailable. This paper presents an independent, simple and robust method to retrieve the FOV of an instrument during operation, i.e. the two-dimensional sensitivity distribution, sampled on a discrete grid. The method relies on correlated measurements featuring a significantly higher spatial resolution, e.g. by an imaging instrument accompanying a spectrometer. The method was applied to two satellite instruments, GOME-2 and OMI, and a ground-based differential optical absorption spectroscopy (DOAS) instrument integrated in an SO2 camera. For GOME-2, quadrangular FOVs could be retrieved, which almost perfectly match the provided FOV edges after applying a correction for spatial aliasing inherent to GOME-type instruments. More complex sensitivity distributions were found at certain scanner angles, which are probably caused by degradation of the moving parts within the instrument. For OMI, which does not feature any moving parts, retrieved sensitivity distributions were much smoother compared to GOME-2. A 2-D super-Gaussian with six parameters was found to be an appropriate model to describe the retrieved OMI FOV. The comparison with operationally provided FOV dimensions revealed small differences, which could be mostly explained by the limitations of our IFR implementation. For the ground-based DOAS instrument, the FOV retrieved using SO2-camera data was slightly smaller than the flat-disc distribution, which is assumed by the state-of-the-art correlation technique. Differences between both methods may be attributed to spatial inhomogeneities. In general, our results confirm the already deduced FOV distributions of OMI, GOME-2, and the ground-based DOAS. It is certainly applicable for degradation monitoring and verification exercises. For satellite instruments, the gained information is expected to increase the accuracy of combined products, where measurements of different instruments are integrated, e.g. mapping of high-resolution cloud information, incorporation of surface climatologies. For the SO2-camera community, the method presents a new and efficient tool to monitor the DOAS FOV in the field.

Description: Heterogeneous photochemistry converts bromide (Br−) to reactive bromine species (Br atoms and bromine monoxide, BrO) that dominate Arctic springtime chemistry. This phenomenon has many impacts such as boundary-layer ozone depletion, mercury oxidation and deposition, and modification of the fate of hydrocarbon species. To study environmental controls on reactive bromine events, the BRomine, Ozone, and Mercury EXperiment (BROMEX) was carried out from early March to mid-April 2012 near Barrow (Utqiaġvik), Alaska. We measured horizontal and vertical gradients in BrO with multiple-axis differential optical absorption spectroscopy (MAX-DOAS) instrumentation at three sites, two mobile and one fixed. During the campaign, a large crack in the sea ice (an open lead) formed pushing one instrument package ∼ 250 km downwind from Barrow (Utqiaġvik). Convection associated with the open lead converted the BrO vertical structure from a surface-based event to a lofted event downwind of the lead influence. The column abundance of BrO downwind of the re-freezing lead was comparable to upwind amounts, indicating direct reactions on frost flowers or open seawater was not a major reactive bromine source. When these three sites were separated by ∼ 30 km length scales of unbroken sea ice, the BrO amount and vertical distributions were highly correlated for most of the time, indicating the horizontal length scales of BrO events were typically larger than ∼ 30 km in the absence of sea ice features. Although BrO amount and vertical distribution were similar between sites most of the time, rapid changes in BrO with edges significantly smaller than this ∼ 30 km length scale episodically transported between the sites, indicating BrO events were large but with sharp edge contrasts. BrO was often found in shallow layers that recycled reactive bromine via heterogeneous reactions on snowpack. Episodically, these surface-based events propagated aloft when aerosol extinction was higher (〉 0.1 km−1); however, the presence of aerosol particles aloft was not sufficient to produce BrO aloft. Highly depleted ozone (

Description: In order to promote the development of the passive DOAS technique the Multi Axis DOAS – Comparison campaign for Aerosols and Trace gases (MAD-CAT) was held at the Max Planck Institute for Chemistry in Mainz, Germany, from June to October 2013. Here, we systematically compare the differential slant column densities (dSCDs) of nitrous acid (HONO) derived from measurements of seven different instruments. We also compare the tropospheric difference of SCDs (delta SCD) of HONO, namely the difference of the SCDs for the non-zenith observations and the zenith observation of the same elevation sequence. Different research groups analysed the spectra from their own instruments using their individual fit software. All the fit errors of HONO dSCDs from the instruments with cooled large-size detectors are mostly in the range of 0.1 to 0.3  ×  1015 molecules cm−2 for an integration time of 1 min. The fit error for the mini MAX-DOAS is around 0.7  ×  1015 molecules cm−2. Although the HONO delta SCDs are normally smaller than 6  ×  1015 molecules cm−2, consistent time series of HONO delta SCDs are retrieved from the measurements of different instruments. Both fits with a sequential Fraunhofer reference spectrum (FRS) and a daily noon FRS lead to similar consistency. Apart from the mini-MAX-DOAS, the systematic absolute differences of HONO delta SCDs between the instruments are smaller than 0.63  ×  1015 molecules cm−2. The correlation coefficients are higher than 0.7 and the slopes of linear regressions deviate from unity by less than 16 % for the elevation angle of 1°. The correlations decrease with an increase in elevation angle. All the participants also analysed synthetic spectra using the same baseline DOAS settings to evaluate the systematic errors of HONO results from their respective fit programs. In general the errors are smaller than 0.3  ×  1015 molecules cm−2, which is about half of the systematic difference between the real measurements.The differences of HONO delta SCDs retrieved in the selected three spectral ranges 335–361, 335–373 and 335–390 nm are considerable (up to 0.57  ×  1015 molecules cm−2) for both real measurements and synthetic spectra. We performed sensitivity studies to quantify the dominant systematic error sources and to find a recommended DOAS setting in the three spectral ranges. The results show that water vapour absorption, temperature and wavelength dependence of O4 absorption, temperature dependence of Ring spectrum, and polynomial and intensity offset correction all together dominate the systematic errors. We recommend a fit range of 335–373 nm for HONO retrievals. In such fit range the overall systematic uncertainty is about 0.87  ×  1015 molecules cm−2, much smaller than those in the other two ranges. The typical random uncertainty is estimated to be about 0.16  ×  1015 molecules cm−2, which is only 25 % of the total systematic uncertainty for most of the instruments in the MAD-CAT campaign. In summary for most of the MAX-DOAS instruments for elevation angle below 5°, half daytime measurements (usually in the morning) of HONO delta SCD can be over the detection limit of 0.2  ×  1015 molecules cm−2 with an uncertainty of  ∼  0.9  ×  1015 molecules cm−2.

Description: Water vapour is known to absorb radiation from the microwave region to the blue part of the visible spectrum with decreasing efficiency. Ab initio approaches to model individual absorption lines of the gaseous water molecule predict absorption lines up to its dissociation limit at 243 nm.We present the first evidence of water vapour absorption near 363 nm from field measurements using data from multi-axis differential optical absorption spectroscopy (MAX-DOAS) and long-path (LP)-DOAS measurements. The identification of the absorptions was based on the recent POKAZATEL line list by Polyansky et al. (2017). For MAX-DOAS measurements, we observed absorption by water vapour in an absorption band around 363 nm with optical depths of up to 2 × 10−3. The retrieved column densities from 2 months of measurement data and more than 2000 individual observations at different latitudes correlate well with simultaneously measured well-established water vapour absorptions in the blue spectral range from 452 to 499 nm (R2 = 0.89), but the line intensities at around 363 nm are underestimated by a factor of 2.6  ±  0.5 by the ab initio model. At a spectral resolution of 0.5 nm, we derive a maximum cross section value of 2.7 × 10−27 cm2 molec−1 at 362.3 nm. The results were independent of the used literature absorption cross section of the O4 absorption, which overlays this water vapour absorption band. Also water vapour absorption around 376 nm was identified. Below 360 nm no water vapour absorption above 1.4 × 10−26 cm2 molec−1 was observed. The newly found absorption can have a significant impact on the spectral retrievals of absorbing trace-gas species in the spectral range around 363 nm. Its effect on the spectral analysis of O4, HONO and OClO is discussed.