Abstract. In 1997 the International Maritime Organisation (IMO) adopted MARPOL Annex VI to prevent air pollution by shipping emissions. It regulates, among other issues, the sulfur content in shipping fuels, which is transformed into the air pollutant sulfur dioxide (SO 2 ) during combustion. Within designated Sulfur Emission Control Areas (SECA), the sulfur content was limited to 1 %, and on 1 January 2015, this limit was further reduced to 0.1 %. Here we present the set-up and measurement results of a permanent ship emission monitoring site near Hamburg harbour in the North Sea SECA. Trace gas measurements are conducted with in situ instruments and a data set from September 2014 to January 2015 is presented. By combining measurements of carbon dioxide (CO 2 ) and SO 2 with ship position data, it is possible to deduce the sulfur fuel content of individual ships passing the measurement station, thus facilitating the monitoring of compliance of ships with the IMO regulations. While compliance is almost 100 % for the 2014 data, it decreases only very little in 2015 to 95.4 % despite the much stricter limit. We analysed more than 1400 ship plumes in total and for months with favourable conditions, up to 40 % of all ships entering and leaving Hamburg harbour could be checked for their sulfur fuel content.

Abstract. In this study we report on airborne imaging DOAS measurements of NO 2 from two flights performed in Bucharest during the AROMAT campaign (Airborne ROmanian Measurements of Aerosols and Trace gases) in September 2014. These measurements were performed with the Airborne imaging Differential Optical Absorption Spectroscopy (DOAS) instrument for Measurements of Atmospheric Pollution (AirMAP) and provide nearly gapless maps of column densities of NO 2 below the aircraft with a high spatial resolution of better than 100 m. The air mass factors, which are needed to convert the measured differential slant column densities (dSCDs) to vertical column densities (VCDs), have a strong dependence on the surface reflectance, which has to be accounted for in the retrieval. This is especially important for measurements above urban areas, where the surface properties vary strongly. As the instrument is not radiometrically calibrated, we have developed a method to derive the surface reflectance from intensities measured by AirMAP. This method is based on radiative transfer calculation with SCIATRAN and a reference area for which the surface reflectance is known. While surface properties are clearly apparent in the NO 2 dSCD results, this effect is successfully corrected for in the VCD results. Furthermore, we investigate the influence of aerosols on the retrieval for a variety of aerosol profiles that were measured in the context of the AROMAT campaigns. The results of two research flights are presented, which reveal distinct horizontal distribution patterns and strong spatial gradients of NO 2 across the city. Pollution levels range from background values in the outskirts located upwind of the city to about 4 × 10 16 molec cm −2 in the polluted city center. Validation against two co-located mobile car-DOAS measurements yields good agreement between the datasets, with correlation coefficients of R = 0.94 and R = 0.85, respectively. Estimations on the NO x emission rate of Bucharest for the two flights yield emission rates of 15.1 ± 9.4 and 13.6 ± 8.4 mol s −1 , respectively.

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.

Abstract. A 3-year time series of ground-based multi-axis differential optical absorption spectroscopy (MAX-DOAS) measurements of NO2 and SO2 on the island Neuwerk has been analyzed for contributions from shipping emissions. The island is located in the German Bight, close to the main shipping lane (at a distance of 6–7 km) into the river Elbe towards the harbor of Hamburg. Measurements of individual ship plumes as well as of background pollution are possible from this location. A simple approach using the column amounts of the oxygen molecule dimer or collision complex, O4, for the determination of the horizontal light path length has been applied to retrieve path-averaged volume mixing ratios. An excellent agreement between mixing ratios determined from NO2 retrievals in the UV and visible parts of the spectrum has been found, showing the validity of the approach. Obtained mixing ratios of NO2 and SO2 are compared to co-located in situ measurements showing good correlation on average but also a systematic underestimation by the MAX-DOAS O4 scaling approach. Comparing data before and after the introduction of stricter fuel sulfur content limits (from 1 to 0.1 %) on 1 January 2015 in the North Sea Emission Control Area (ECA), a significant reduction in SO2 levels is observed. For situations with wind from the open North Sea, where ships are the only local source of air pollution, the average mixing ratio of SO2 decreased by a factor of 8, while for NO2 in the whole time series from 2013 to 2016, no significant change in emissions was observed. More than 2000 individual ship emission plumes have been identified in the data and analyzed for the emission ratio of SO2 to NO2, yielding an average ratio of 0.3 for the years 2013/2014 and decreasing significantly, presumably due to lower fuel sulfur content, in 2015/2016. By sorting measurements according to the prevailing wind direction and selecting two angular reference sectors representative for wind from the open North Sea and coast excluding data with mixed air mass origin, relative contributions of ships and land-based sources to air pollution levels in the German Bight have been estimated to be around 40 % : 60 % for NO2 as well as SO2 in 2013/2014, dropping to 14 % : 86 % for SO2 in 2015/2016.

Abstract. 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 × 10 15 molecules cm −2 for an integration time of 1 min. The fit error for the mini MAX-DOAS is around 0.7 × 10 15 molecules cm −2 . Although the HONO delta SCDs are normally smaller than 6 × 10 15 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 × 10 15 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 toPublished by Copernicus Publications on behalf of the European Geosciences Union. Y. Wang et al.: MAX-DOAS measurements of HONO slant column densitiesevaluate the systematic errors of HONO results from their respective fit programs. In general the errors are smaller than 0.3 × 10 15 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 × 10 15 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 O 4 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 × 10 15 molecules cm −2 , much smaller than those in the other two ranges. The typical random uncertainty is estimated to be about 0.16 × 10 15 molecules cm −2 , which is only 25 % of the total syst...