ALBERT

Description: Absolute radiometric calibrations are important for measurements of the atmospheric spectral radiance. Such measurements can be used to determine actinic fluxes, the properties of aerosols and clouds and the short wave energy budget. Conventional calibration methods in the laboratory are based on calibrated light sources and reflectors and are expensive, time consuming and subject to relatively large uncertainties. Also, the calibrated instruments might change during transport from the laboratory to the measurement sites. Here we present a new calibration method for UV/vis instruments that measure the spectrally resolved sky radiance, like for example zenith sky Differential Optical Absorption Spectroscopy (DOAS-) instruments or Multi-AXis (MAX-) DOAS instruments. Our method is based on the comparison of the solar zenith angle dependence of the measured zenith sky radiance with radiative transfer simulations. For the application of our method clear sky measurements during periods with almost constant aerosol optical depth are needed. The radiative transfer simulations have to take polarisation into account. We show that the calibration results are almost independent from the knowledge of the aerosol optical properties and surface albedo, which causes a rather small uncertainty of about

Description: Multi-Axis-Differential Optical Absorption Spectroscopy (MAX-DOAS) observations of trace gases can be strongly influenced by clouds and aerosols. Thus it is important to identify clouds and characterise their properties. In a recent study Wagner et al. (2014) developed a cloud classification scheme based on the MAX-DOAS measurements themselves with which different "sky conditions" (e.g. clear sky, continuous clouds, broken clouds) can be distinguished. Here we apply this scheme to long term MAX-DOAS measurements from 2011 to 2013 in Wuxi, China (31.57° N, 120.31° E). The original algorithm has been modified, in particular in order to account for smaller solar zenith angles (SZA). Instrumental degradation is accounted for to avoid artificial trends of the cloud classification. We compared the results of the MAX-DOAS cloud classification scheme to several independent measurements: aerosol optical depth from a nearby AERONET station and from MODIS, visibility derived from a visibility meter; and various cloud parameters from different satellite instruments (MODIS, OMI, and GOME-2). The most important findings from these comparisons are: (1) most cases characterized as clear sky with low or high aerosol load were associated with the respective AOD ranges obtained by AERONET and MODIS, (2) the observed dependences of MAX-DOAS results on cloud optical thickness and effective cloud fraction from satellite indicate that the cloud classification scheme is sensitive to cloud (optical) properties, (3) separation of cloudy scenes by cloud pressure shows that the MAX-DOAS cloud classification scheme is also capable of detecting high clouds, (4) some clear sky conditions, especially with high aerosol load, classified from MAX-DOAS observations corresponding to the optically thin and low clouds derived by satellite observations probably indicate that the satellite cloud products contain valuable information on aerosols.

Description: The STRatospheric Estimation Algorithm from Mainz (STREAM) determines stratospheric columns of NO2 which are needed for the retrieval of tropospheric columns from satellite observations. It is based on the total column measurements over clean, remote regions as well as over clouded scenes where the tropospheric column is effectively shielded. The contribution of individual satellite measurements to the stratospheric estimate is controlled by various weighting factors. STREAM is a flexible and robust algorithm and does not require input from chemical transport models. It was developed as verification algorithm for the upcoming satellite instrument TROPOMI, as complement to the operational stratospheric correction based on data assimilation. STREAM was successfully applied to the UV/vis satellite instruments GOME 1/2, SCIAMACHY, and OMI. It overcomes some of the artefacts of previous algorithms, as it is capable of reproducing gradients of stratospheric NO2, e.g. related to the polar vortex, and reduces interpolation errors over continents. Based on synthetic input data, the uncertainty of STREAM was quantified as about 0.1–0.2 × 1015 molecules cm−2, in accordance to the typical deviations between stratospheric estimates from different algorithms compared in this study.

Description: We compare tropospheric column densities (vertically integrated concentrations) of NO2 from three data sets for the metropolitan area of Paris during two extensive measurement campaigns (25 days in summer 2009 and 29 days in winter 2010) within the European research project MEGAPOLI. The selected data sets comprise a regional chemical transport model (CHIMERE) as well as two observational data sets: ground based mobile Multi-AXis-Differential Optical Absorption Spectroscopy (car-MAX-DOAS) measurements and satellite measurements from the Ozone Monitoring Instrument (OMI). On most days, car-MAX-DOAS measurements were carried out along large circles (diameter ~35 km) around Paris. The car-MAX-DOAS results are compared to coincident data from CHIMERE and OMI. All three data sets have their specific strengths and weaknesses, especially with respect to their spatio-temporal resolution and coverage as well as their uncertainties. Thus we compare them in two different ways: first, we simply consider the original data sets. Second, we compare modified versions making synergistic use of the complementary information from different data sets. For example, profile information from the regional model is used to improve the satellite data, observations of the horizontal trace gas distribution are used to adjust the respective spatial patterns of the model simulations, or the model is used as a transfer tool to bridge the spatial scales between car-MAX-DOAS and satellite observations. Using the modified versions of the data sets, the comparison results substantially improve compared to the original versions. In general, good agreement between the data sets is found outside the emission plume, but inside the emission plumes the tropospheric NO2 VCDs are systematically underestimated by the CHIMERE model and the satellite observations (compared to the car-MAX-DOAS observations). One major result from our study is that for satellite validation close to strong emission sources (like power plants or megacities) detailed information about the intra-pixel heterogeneity is essential. Such information may be gained from simultaneous car-MAX-DOAS measurements using multiple instruments or by combining (car-) MAX-DOAS measurements with results from regional model simulations.

Description: A first direct intercomparison of aerosol vertical profiles from Multi-Axis Differential Optical Absorption Spectroscopy (MAX-DOAS) observations, performed during the Cabauw Intercomparison Campaign of Nitrogen Dioxide measuring Instruments (CINDI) in summer 2009, is presented. Five out of 14 participants of the CINDI campaign reported aerosol extinction profiles and aerosol optical thickness (AOT) as deduced from observations of differential slant column densities of the oxygen collision complex (O4) at different elevation angles. Aerosol vertical profiles and AOT are compared to backscatter profiles from a ceilometer instrument and to sun photometer measurements, respectively. Furthermore, the near-surface aerosol extinction coefficient is compared to in-situ measurements of a humidity controlled nephelometer and dry aerosol absorption measurements. The participants of this intercomparison exercise use different approaches for the retrieval of aerosol information, including the retrieval of the full vertical profile using optimal estimation and a parametrised approach with a prescribed profile shape. Despite these large conceptual differences, and also differences in the wavelength of the observed O4 absorption band, good agreement in terms of the vertical structure of aerosols within the boundary layer is achieved between the aerosol extinction profiles retrieved by the different groups and the backscatter profiles observed by the ceilometer instrument. AOT from MAX-DOAS and sun photometer show a good correlation (R 〉 0.8), but all participants systematically underestimate the AOT. Substantial differences between the near-surface aerosol extinction from MAX-DOAS and from the humidified nephelometer remain largely unresolved.

Description: We present a new method to quantify NOx emissions and corresponding atmospheric lifetimes from OMI NO2 observations together with ECMWF wind fields without further model input for sources located in polluted background. NO2 patterns under calm wind conditions are used as proxy for the spatial patterns of NOx emissions, and the effective atmospheric NOx lifetime is determined from the change of spatial patterns measured at larger wind speeds. Emissions are subsequently derived from the NO2 mass above background integrated around the source of interest. Lifetimes and emissions are estimated for 17 power plants and 53 cities located in non-mountainous regions across China and the US. The derived lifetimes for non-mountainous sites are 3.8 ± 1.0 h on average with ranges of 1.8 to 7.5 h. The derived NOx emissions show generally good agreement with bottom-up inventories for power plants and cities. Global inventory significantly underestimated NOx emissions in Chinese cities, most likely due to uncertainties associated with downscaling approaches.

Description: We present a top-down approach to infer and quantify rain-induced emission pulses of NOx (≡ NO + NO2), stemming from biotic emissions of NO from soils, globally with a spatial resolution of 0.25° from satellite-borne measurements of NO2. This is achieved by synchronizing time series at single grid pixels according to the first day of rain after a dry spell of prescribed duration. The full track of the temporal evolution several weeks before and after a rain pulse is retained with daily resolution. These are needed for a sophisticated background correction, which accounts for seasonal variations in the time series and allows for improved quantification of rain-induced soil emissions. We find strong peaks of enhanced NO2 Vertical Column Densities (VCDs) on the first day of rainfall after prolonged droughts in many semi-arid regions of the world, in particular in the Sahel. Detailed investigations show that the rain-induced NO2 pulse detected by the OMI, GOME-2 and SCIAMACHY satellite instruments could not be explained by other sources, such as biomass burning or lightning, or by retrieval artefacts (e.g. due to clouds). For the Sahel region, absolute enhancements of the NO2 VCDs on the first day of rain based on OMI measurements 2007–2010 are on average 4 × 1014 molec cm−2 and exceed 1 × 1015 molec cm−2 for individual grid cells. Assuming a NOx lifetime of 4 h, this corresponds to soil NOx emissions in the range of 6 ng N m−2 s−1 up to 65 ng N m−2 s−1, in good agreement with literature values. Apart from the clear first-day peak, NO2 VCDs show moderately enhanced NO2 VCDs of 2 × 1014 molec cm−2 compared to background over the following two weeks suggesting potential further emissions during that period of about 3.3 ng N m−2 s−1.

Description: The Rann of Kutch (India/Pakistan) is one of the largest salt deserts in the world. Being a so-called 'seasonal salt marsh', it is regularly flooded during the Indian Summer Monsoon. We present 10 years of bromine monoxide (BrO) satellite observations by the Ozone Monitoring Instrument (OMI) over the Great and Little Rann of Kutch. OMI spectra were analysed using Differential Optical Absorption Spectroscopy (DOAS) and revealed recurring high BrO VCDs up to 1.4 × 1014 molec/cm2 during April/May, but no significantly enhanced column densities during the monsoon season (June–September). In the following winter months, the BrO VCDs are again slightly enhanced while the salty surface dries up. We investigate a possible correlation of enhanced reactive bromine concentrations with different meteorological parameters and find a strong relationship between incident UV radiation and the total BrO abundance. In contrast, the second Global Ozone Monitoring Instrument (GOME-2) shows about four times lower BrO VCDs over the Rann of Kutch than found by OMI and no clear seasonal cycle is observed. One reason for this finding might be the earlier local overpass time of GOME-2 compared to OMI (around 9:30 vs. 13:30 LT), as the ambient conditions significantly differ for both satellite instruments at the time of the measurements. Further possible reasons are discussed and mainly attributed to instrumental issues. OMI additionally confirms the presence of enhanced BrO concentrations over the Dead Sea valley (Israel/Jordan), as suggested by former ground-based observations. The measurements indicate that the Rann of Kutch salt marsh is probably one of the strongest natural point sources of reactive bromine compounds outside the polar regions and is therefore supposed to have an significant impact on local and regional ozone chemistry.

Description: A study was carried out to understand the contributions of soil biogenic NO emissions from managed (fertilized and irrigated) hyper-arid ecosystem in NW-China to the regional NO2 emissions during growing season. Soil biogenic NO emissions were quantified by laboratory incubation of corresponding soil samples. We have developed the Geoscience General Tool Package (GGTP) to obtain soil temperature, soil moisture and biogenic soil NO emission at oasis scale. Bottom-up anthropogenic NO2 emissions have been scaled down from annual to monthly values to compare mean monthly soil biogenic NO2 emissions. The top-down emission estimates have been derived from satellite observations compared then with the bottom-up emission estimates (anthropogenic and biogenic). The results show that the soil biogenic emissions of NO2 during the growing period are (at least) equal until twofold of the related anthropogenic sources. We found that the grape soils are the main summertime contributor to the biogenic NO emissions of study area, followed by cotton soils. The top-down and bottom-up emission estimates were shown to be useful methods to estimate the monthly/seasonal cycle of the total regional NO2 emissions. The resulting total NO2 emissions show a strong peak in winter and a secondary peak in summer, providing confidence in the method. These findings provide strong evidence that biogenic emissions from soils of managed drylands (irrigated and fertilized) in the growing period can be much more important contributors to the regional NO2 budget (hence to regional photochemistry) of dryland regions than thought before.

Description: We characterize the temporal variation and spatial distribution of nitrogen dioxide (NO2), sulphur dioxide (SO2), formaldehyde (HCHO) and aerosol extinctions using vertical profiles derived from long-term Multi Axis – Differential Optical Absorption Spectroscopy (MAX-DOAS) observations from May 2011 to November 2014 in Wuxi, China. A new inversion algorithm (PriAM) is implemented to retrieve profiles of the trace gases (TGs) and aerosol extinction (AE) from the UV spectra of scattered sunlight recorded by the MAX-DOAS instrument. We investigated two important aspects of the retrieval process. We found that the systematic seasonal variation of temperature and pressure (which is regularly observed in Wuxi) can lead to a systematic bias of the retrieved aerosol profiles (e.g. up 20 % for the AOD) if it is not explicitly considered. In this study we take this effect for the first time into account. We also investigated in detail the reason for the differences of tropospheric VCDs derived from either the geometric approximation or by the integration of the retrieved profiles, which were reported by earlier studies. We found that these differences are almost entirely caused by the limitations of the geometric approximation (especially for high aerosol loads). The results retrieved from the MAX-DOAS observations are compared with independent techniques not only under cloud free sky conditions, but also under various cloud scenarios. Under most cloudy conditions (except fog and optically thick clouds), the trace gas results still show good agreement. In contrast, from the aerosol results only near-surface AEs could be still well retrieved under cloudy situations. After a quality controlling procedure, the MAX-DOAS data are used to characterize the seasonal, diurnal, and weekly variations of NO2, SO2, HCHO and aerosols. A regular seasonality of the three trace gases is found, but not for aerosols. Similar diurnal variations are found for SO2, HCHO and aerosols in different seasons, but not for NO2. Similar annual variations of the profiles are found in different years, especially for the trace gases. Considerable amplitudes of weekly cycles occur for NO2 and SO2, but not for HCHO and aerosols. Good correlations between the TGs and aerosols are found, especially for HCHO in winter. Significant wind direction dependencies of the trace gases, especially for the near-surface concentrations, are found, but only a weak dependence is found for aerosol properties, especially the AOD. Our findings imply that the local emissions from the industrial area (including traffic emissions) dominate the amount of local pollutants while long distance transport might also considerably contribute to the local aerosol levels.