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.

Multi-axis differential optical absorption spectroscopy (MAX-DOAS) and direct sun NO₂ vertical column network data are used to investigate the accuracy of tropospheric NO₂ column measurements of the GOME-2 instrument on the MetOp-A satellite platform and the OMI instrument on Aura. The study is based on 23 MAX-DOAS and 16 direct sun instruments at stations distributed worldwide. A method to quantify and correct for horizontal dilution effects in heterogeneous NO₂ field conditions is proposed. After systematic application of this correction to urban sites, satellite measurements are found to present smaller biases compared to ground-based reference data in almost all cases. We investigate the seasonal dependence of the validation results as well as the impact of using different approaches to select satellite ground pixels in coincidence with ground-based data. In optimal comparison conditions (satellite pixels containing the station) the median bias between satellite tropospheric NO₂ column measurements and the ensemble of MAX-DOAS and direct sun measurements is found to be significant and equal to −34 % for GOME-2A and −24 % for OMI. These biases are further reduced to −24 % and −18 % respectively, after application of the dilution correction. Comparisons with the QA4ECV satellite product for both GOME-2A and OMI are also performed, showing less scatter but also a slightly larger median tropospheric NO₂ column bias with respect to the ensemble of MAX-DOAS and direct sun measurements.

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) $\times {\mathrm{10}}^{\mathrm{14}}\mathrm{molec}.{\mathrm{cm}}^{-\mathrm{2}}$ for trace gas (NO₂, HCHO) VCDs and (0.3–$\mathrm{8})\times {\mathrm{10}}^{\mathrm{10}}\mathrm{molec}.{\mathrm{cm}}^{-\mathrm{3}}$ for trace gas surface concentrations. These values compare to approximate average optical thicknesses of 0.3, trace gas vertical columns of $\mathrm{90}\times {\mathrm{10}}^{\mathrm{14}}\mathrm{molec}.{\mathrm{cm}}^{-\mathrm{2}}$ and trace gas surface concentrations of $\mathrm{11}\times {\mathrm{10}}^{\mathrm{10}}\mathrm{molec}.{\mathrm{cm}}^{-\mathrm{3}}$ 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–$\mathrm{55})\times {\mathrm{10}}^{\mathrm{14}}\mathrm{molec}.{\mathrm{cm}}^{-\mathrm{2}}$ against trace gas VCDs from direct-sun DOAS observations and (0.8–$\mathrm{9})\times {\mathrm{10}}^{\mathrm{10}}\mathrm{molec}.{\mathrm{cm}}^{-\mathrm{3}}$ 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.

One of the main issues arising from the comparison of ground-based and satellite measurements is the difference in spatial representativeness, which for locations with inhomogeneous spatial distribution of pollutants may lead to significant differences between the two data sets. In order to investigate the spatial variability of tropospheric NO₂ within a sub-satellite pixel, a campaign which lasted for about 6 months was held in the greater area of Thessaloniki, Greece. Three multi-axial differential optical absorption spectroscopy (MAX-DOAS) systems performed measurements of tropospheric NO₂ columns at different sites representative of urban, suburban and rural conditions. The direct comparison of these ground-based measurements with corresponding products from the Ozone Monitoring Instrument onboard NASA's Aura satellite (OMI/Aura) showed good agreement over the rural and suburban areas, while the comparison with the Global Ozone Monitoring Experiment-2 (GOME-2) onboard EUMETSAT's Meteorological Operational satellites' (MetOp-A and MetOp-B) observations is good only over the rural area. GOME-2A and GOME-2B sensors show an average underestimation of tropospheric NO₂ over the urban area of about 10.51 ± 8.32 × 10¹⁵ and 10.21 ± 8.87 × 10¹⁵ molecules cm⁻², respectively. The mean difference between ground-based and OMI observations is significantly lower (6.60 ± 5.71 × 10¹⁵ molecules cm⁻²). The differences found in the comparisons of MAX-DOAS data with the different satellite sensors can be attributed to the higher spatial resolution of OMI, as well as the different overpass times and NO₂ retrieval algorithms of the satellites. OMI data were adjusted using factors calculated by an air quality modeling tool, consisting of the Weather Research and Forecasting (WRF) mesoscale meteorological model and the Comprehensive Air Quality Model with Extensions (CAMx) multiscale photochemical transport model. This approach resulted in significant improvement of the comparisons over the urban monitoring site. The average difference of OMI observations from MAX-DOAS measurements was reduced to −1.68 ± 5.01 × 10¹⁵ molecules cm⁻².

In this study, we present an aerosol classification technique based on measurements of a double monochromator Brewer spectrophotometer during the period 1998–2017 in Thessaloniki, Greece. A machine learning clustering procedure was applied based on the Mahalanobis distance metric. The classification process utilizes the UV Single Scattering Albedo (SSA) at 340 nm and the Extinction Angstrom Exponent (EAE) at 320–360 nm that are obtained from the spectrophotometer. The analysis is supported by measurements from a CIMEL sunphotometer that were deployed in order to establish the training dataset of Brewer measurements. By applying the Mahalanobis distance algorithm to the Brewer timeseries, we automatically assigned measurements in one of the following clusters: Fine Non Absorbing Mixtures (FNA): 64.7%, Black Carbon Mixtures (BC): 17.4%, Dust Mixtures (DUST): 8.1%, and Mixed: 9.8%. We examined the clustering potential of the algorithm by reclassifying the training dataset and comparing it with the original one and also by using manually classified cases. The typing score of the Mahalanobis algorithm is high for all predominant clusters FNA: 77.0%, BC: 63.9%, and DUST: 80.3% when compared with the training dataset. We obtained high scores as well FNA: 100.0%, BC: 66.7%, and DUST: 83.3% when comparing it with the manually classified dataset. The flags obtained here were applied in the timeseries of the Aerosol Optical Depth (AOD) at 340 nm of the Brewer and the CIMEL in order to compare between the two and also stress the future impact of the proposed clustering technique in climatological studies of the station.

The gap in knowledge regarding the radiative effects of aerosols in the UV region of the solar spectrum is large, mainly due to the lack of systematic measurements of the aerosol single scattering albedo (SSA) and absorption optical depth (AAOD). In the present study, spectral UV measurements performed in Thessaloniki, Greece by a double monochromator Brewer spectrophotometer in the period 1998–2017 are used for the calculation of the aforementioned optical properties. The main uncertainty factors have been described and there is an effort to quantify the overall uncertainties in SSA and AAOD. Analysis of the results suggests that the absorption by aerosols is much stronger in the UV relative to the visible. SSA follows a clear annual pattern ranging from ~0.7 in winter to ~0.85 in summer at wavelengths 320–360 nm, while AAOD peaks in summer and winter. The average AAOD for 2009–2011 is ~50% above the 2003–2006 average, possibly due to increased emissions of absorbing aerosols related to the economic crisis and the metro-railway construction works in the city center.