Abstract. Global observations of tropospheric nitrogen dioxide (NO2) columns have been shown to be feasible from space, but consistent multi-sensor records do not yet exist, nor are they covered by planned activities at the international level. Harmonised, multi-decadal records of NO2 columns and their associated uncertainties can provide crucial information on how the emissions and concentrations of nitrogen oxides evolve over time. Here we describe the development of a new, community best-practice NO2 retrieval algorithm based on a synthesis of existing approaches. Detailed comparisons of these approaches led us to implement an enhanced spectral fitting method for NO2, a 1°  ×  1° TM5-MP data assimilation scheme to estimate the stratospheric background and improve air mass factor calculations. Guided by the needs expressed by data users, producers, and WMO GCOS guidelines, we incorporated detailed per-pixel uncertainty information in the data product, along with easily traceable information on the relevant quality aspects of the retrieval. We applied the improved QA4ECV NO2 algorithm to the most current level-1 data sets to produce a complete 22-year data record that includes GOME (1995–2003), SCIAMACHY (2002–2012), GOME-2(A) (2007 onwards) and OMI (2004 onwards). The QA4ECV NO2 spectral fitting recommendations and TM5-MP stratospheric column and air mass factor approach are currently also applied to S5P-TROPOMI. The uncertainties in the QA4ECV tropospheric NO2 columns amount to typically 40 % over polluted scenes. The first validation results of the QA4ECV OMI NO2 columns and their uncertainties over Tai'an, China, in June 2006 suggest a small bias (−2 %) and better precision than suggested by uncertainty propagation. We conclude that our improved QA4ECV NO2 long-term data record is providing valuable information to quantitatively constrain emissions, deposition, and trends in nitrogen oxides on a global scale.

Abstract. In June 2009, 22 spectrometers from 14 institutes measured tropospheric and stratospheric NO 2 from the ground for more than 11 days during the Cabauw Intercomparison Campaign of Nitrogen Dioxide measuring Instruments (CINDI), at Cabauw, NL (51.97 • N, 4.93 • E). All visible instruments used a common wavelength range and set of cross sections for the spectral analysis. Most of the instruments were of the multi-axis design with analysis by differential spectroscopy software (MAX-DOAS), whose nonzenith slant columns were compared by examining slopes of their least-squares straight line fits to mean values of a selection of instruments, after taking 30-min averages. Zenith slant columns near twilight were compared by fits Correspondence to: H. K. Roscoe (h.roscoe@bas.ac.uk) to interpolated values of a reference instrument, then normalised by the mean of the slopes of the best instruments. For visible MAX-DOAS instruments, the means of the fitted slopes for NO 2 and O 4 of all except one instrument were within 10% of unity at almost all non-zenith elevations, and most were within 5%. Values for UV MAX-DOAS instruments were almost as good, being 12% and 7%, respectively. For visible instruments at zenith near twilight, the means of the fitted slopes of all instruments were within 5% of unity. This level of agreement is as good as that of previous intercomparisons, despite the site not being ideal for zenith twilight measurements. It bodes well for the future of measurements of tropospheric NO 2 , as previous intercomparisons were only for zenith instruments focussing on stratospheric NO 2 , with their longer heritage.Published by Copernicus Publications on behalf of the European Geosciences Union.

Abstract. On board the Copernicus Sentinel-5 Precursor (S5P) platform, the TROPOspheric Monitoring Instrument (TROPOMI) is a double-channel, nadir-viewing grating spectrometer measuring solar back-scattered earthshine radiances in the ultraviolet, visible, near-infrared, and shortwave infrared with global daily coverage. In the ultraviolet range, its spectral resolution and radiometric performance are equivalent to those of its predecessor OMI, but its horizontal resolution at true nadir is improved by an order of magnitude. This paper introduces the formaldehyde (HCHO) tropospheric vertical column retrieval algorithm implemented in the S5P operational processor and comprehensively describes its various retrieval steps. Furthermore, algorithmic improvements developed in the framework of the EU FP7-project QA4ECV are described for future updates of the processor. Detailed error estimates are discussed in the light of Copernicus user requirements and needs for validation are highlighted. Finally, verification results based on the application of the algorithm to OMI measurements are presented, demonstrating the performances expected for TROPOMI.

Abstract. Nitrogen dioxide (NO2) and formaldehyde (HCHO) column data from satellite instruments are used for air quality and climate studies. Both NO2 and HCHO have been identified as precursors to the ozone (O3) and aerosol essential climate variables, and it is essential to quantify and characterise their uncertainties. Here we present an intercomparison of NO2 and HCHO slant column density (SCD) retrievals from four different research groups (BIRA-IASB, IUP Bremen, and KNMI as part of the Quality Assurance for Essential Climate Variables (QA4ECV) project consortium, and NASA) and from the OMI and GOME-2A instruments. Our evaluation is motivated by recent improvements in differential optical absorption spectroscopy (DOAS) fitting techniques and by the desire to provide a fully traceable uncertainty budget for the climate data record generated within QA4ECV. The improved NO2 and HCHO SCD values are in close agreement but with substantial differences in the reported uncertainties between groups and instruments. To check the DOAS uncertainties, we use an independent estimate based on the spatial variability of the SCDs within a remote region. For NO2, we find the smallest uncertainties from the new QA4ECV retrieval (0.8  ×  1015 molec. cm−2 for both instruments over their mission lifetimes). Relative to earlier approaches, the QA4ECV NO2 retrieval shows better agreement between DOAS and statistical uncertainty estimates, suggesting that the improved QA4ECV NO2 retrieval has reduced but not altogether eliminated systematic errors in the fitting approach. For HCHO, we reach similar conclusions (QA4ECV uncertainties of 8–12  ×  1015 molec. cm−2), but the closeness between the DOAS and statistical uncertainty estimates suggests that HCHO uncertainties are indeed dominated by random noise from the satellite's level 1 data. We find that SCD uncertainties are smallest for high top-of-atmosphere reflectance levels with high measurement signal-to-noise ratios. From 2005 to 2015, OMI NO2 SCD uncertainties increase by 1–2 % year−1, which is related to detector degradation and stripes, but OMI HCHO SCD uncertainties are remarkably stable (increase  <  1 % year−1) and this is related to the use of Earth radiance reference spectra which reduces stripes. For GOME-2A, NO2 and HCHO SCD uncertainties increased by 7–9 and 11–15 % year−1 respectively up until September 2009, when heating of the instrument markedly reduced further throughput loss, stabilising the degradation of SCD uncertainty to  <  3 % year−1 for 2009–2015. Our work suggests that the NO2 SCD uncertainty largely consists of a random component ( ∼  65 % of the total uncertainty) as a result of the propagation of measurement noise but also of a substantial systematic component ( ∼  35 % of the total uncertainty) mainly from stripe effects. Averaging over multiple pixels in space and/or time can significantly reduce the SCD uncertainties. This suggests that trend detection in OMI, GOME-2 NO2, and HCHO time series is not limited by the spectral fitting but rather by the adequacy of assumptions on the atmospheric state in the later air mass factor (AMF) calculation step.

Abstract. A latitudinal cross-section and vertical profiles of iodine monoxide (IO) are reported from the marine boundary layer of the Western Pacific. The measurements were taken using Multi-Axis Differential Optical Absorption Spectroscopy (MAX-DOAS) during the TransBrom cruise of the German research vessel Sonne, which led from Tomakomai, Japan (42° N, 141° E) through the Western Pacific to Townsville, Australia (19° S, 146° E) in October 2009. In the marine boundary layer within the tropics (between 20° N and 5° S), IO mixing ratios ranged between 1 and 2.2 ppt, whereas in the subtropics and at mid-latitudes typical IO mixing ratios were around 1 ppt in the daytime. The profile retrieval reveals that the bulk of the IO was located in the lower part of the marine boundary layer. Photochemical simulations indicate that the organic iodine precursors observed during the cruise (CH3I, CH2I2, CH2ClI, CH2BrI) are not sufficient to explain the measured IO mixing ratios. Reasonable agreement between measured and modelled IO can only be achieved if an additional sea-air flux of inorganic iodine (e.g., I2) is assumed in the model. Our observations add further evidence to previous studies that reactive iodine is an important oxidant in the marine boundary layer.