14 pags., 10 figs. ; Iodine plays a vital role in oxidation chemistry over Antarctica, with past observations showing highly elevated levels of iodine oxide (IO) leading to severe depletion of boundary layer ozone in West Antarctica. Here, we present MAX-DOAS-based (multi-axis differential absorption spectroscopy) observations of IO over three summers (2015-2017) at the Indian Antarctic bases of Bharati and Maitri. IO was observed during all the campaigns with mixing ratios below 2ĝ€¯pptv (parts per trillion by volume) for the three summers, which are lower than the peak levels observed in West Antarctica. This suggests that sources in West Antarctica are different or stronger than sources of iodine compounds in East Antarctica, the nature of which is still uncertain. Vertical profiles estimated using a profile retrieval algorithm showed decreasing gradients with a peak in the lower boundary layer. The ground-based instrument retrieved vertical column densities (VCDs) were approximately a factor of 3 to 5 higher than the VCDs reported using satellite-based instruments, which is most likely related to the sensitivities of the measurement techniques. Air mass back-trajectory analysis failed to highlight a source region, with most of the air masses coming from coastal or continental regions. This study highlights the variation in iodine chemistry in different regions in Antarctica and the importance of a long-term dataset to validate models estimating the impacts of iodine chemistry. ; The ISEA campaigns are organized by the National Centre for Polar and Ocean Research (NCPOR), Ministry of Earth Sciences (MOES), Government of India.IITM and NCPOR are funded by MOES, Government of India.
33 pags., 23 figs., 5 tabs. ; The TROPOspheric Monitoring Instrument(TROPOMI), launched in October 2017 on board the Sentinel-5 Precursor (S5P) satellite, monitors the composition of the Earth's atmosphere at an unprecedented horizontal resolution as fine as 3.5×5.5 km2. This paper assesses the performances of the TROPOMI formaldehyde(HCHO) operational product compared to its predecessor, the OMI (Ozone Monitoring Instrument) HCHO QA4ECV product, at different spatial and temporal scales. The parallel development of the two algorithms favoured the consistency of the products, which facilitates the production of long-term combined time series. The main difference between the two satellite products is related to the use of different cloud algorithms, leading to a positive bias of OMI compared to TROPOMI of up to 30% in tropical regions. We show that after switching off the explicit correction for cloud effects, the two datasets come into an excellent agreement. For medium to large HCHO vertical columns(larger than 5×1015 molec. cm-2) the median bias between OMI and TROPOMI HCHO columns is not larger than 10% (<0.4×1015 molec. cm-2). For lower columns, OMI observations present a remaining positive bias of about 20% (<0.8×1015 molec. cm-2) compared to TROPOMI in midlatitude regions. Here, we also use a global network of 18 MAX-DOAS (multi-axis differential optical absorption spectroscopy) instruments to validate both satellite sensors for a large range of HCHO columns. This work complements the study by Vigouroux et al. (2020), where a global FTIR(Fourier transform infrared) network is used to validate the TROPOMI HCHO operational product. Consistent with the FTIR validation study, we find that for elevated HCHO columns, TROPOMI data are systematically low (-25% for HCHO columns larger than 8 × 1015 molec. cm-2), while no significant bias is found for medium-range column values. We further show that OMI and TROPOMI data present equivalent biases for large HCHO levels. However, TROPOMI significantly improves the precision of the HCHO observations at short temporal scales and for low HCHO columns. We show that compared to OMI, the precision of the TROPOMI HCHO columns is improved by 25% for individual pixels and by up to a factor of 3 when considering daily averages in 20 km radius circles. The validation precision obtained with daily TROPOMI observations is comparable to the one obtained with monthly OMI observations. To illustrate the improved performances of TROPOMI in capturing weak HCHO signals, we present clear detection of HCHO column enhancements related to shipping emissions in the Indian Ocean. This is achieved by averaging data over a much shorter period (3 months) than required with previous sensors (5 years) and opens new perspectives to study shipping emissions of VOCs (volatile organic compounds) and related atmospheric chemical interactions. ; Part of the reported work was carried out in the framework of the Copernicus Sentinel-5 Precursor Mission Performance Centre (S5p MPC), contracted by the European Space Agency (ESA/ESRIN, contract no. 4000117151/16/I-LG) and supported by the Belgian Federal Science Policy Office (BELSPO), the Royal Belgian Institute for Space Aeronomy (BIRA-IASB) and the German Aerospace Centre (DLR). BIRA-IASB acknowledges national funding from BELSPO and ESA through the ProDEx projects TRACE-S5P (TRACE-S5P project) and TROVA. Part of this work was also carried out in the framework of the S5p Validation Team (S5PVT) AO projects NIDFORVAL (ID no. 28607, PI Gaia Pinardi, Corinne Vigouroux, BIRA-IASB). Multi-sensor HCHO developments have been funded by the EU FP7 QA4ECV project (grant no. 607405), in close cooperation with KNMI, University of Bremen, MPIC-Mainz and WUR. Work by Hitoshi Irie was supported by the Environment Research and Technology Development Fund (JPMEERF20192001 and JPMEERF20215005) of the Environmental Restoration and Conservation Agency of Japan, JSPS KAKENHI (grant numbers JP19H04235 and JP20H04320) and the JAXA 2nd Research Announcement on the Earth Observations (grant number 19RT000351).
30 pags., 13 figs., 4 tabs. ; We present the inter-comparison of delta slant column densities (SCDs) and vertical profiles of nitrous acid (HONO) derived from measurements of different multiaxis differential optical absorption spectroscopy (MAXDOAS) 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. cm2, which is half of the typical random discrepancy of 0:6× 1015 molec. cm2. For a typical high HONO delta SCD of 2×1015 molec. cm2, 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 nearsurface volume mixing ratios (VMRs) are mostly in the range of ∼ ±0:5×1014 molec. cm2 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. cm2. 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 MAXDOAS 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. ; Funding for this study was provided by ESA through the CINDI-2 (ESA contract no. 4000118533/16/I-Sbo) and FRM4DOAS (ESA contract no. 4000118181/16/I-EF) projects, by the NSFC (grant no. 41805027), the Russian Foundation for Basic Research (grant no. 18-35-00682), the Russian Academy of Sciences (grant nos. 0150-2018-0052 and 0129-2019- 0002), NASA's Atmospheric Composition Program (grant no. NASA-16-NUP2016-0001), the US National Science Foundation (AGS-1620530 award), and the European Union's Horizon 2020 research and innovation programme through the ACTRIS-2 transnational access programme (grant no. 654109). The AIOFM group is grateful for the support by the NSFC (grant no. 41530644). The article processing charges for this open-access publication were covered by the Max Planck Society
