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In this study the consistency between MAX-DOAS measurements and radiative transfer simulations of the atmospheric O4 absorption is investigated on 2 mainly cloud-free days during the MAD-CAT campaign in Mainz, Germany, in summer 2013. In recent years several studies indicated that measurements and radiative transfer simulations of the atmospheric O4 absorption can only be brought into agreement if a so-called scaling factor (

The Airborne ROmanian Measurements of Aerosols and Trace gases (AROMAT) campaigns took place in Romania in September 2014 and August 2015. They focused on two sites: the Bucharest urban area and large power plants in the Jiu Valley. The main objectives of the campaigns were to test recently developed airborne observation systems dedicated to air quality studies and to verify their applicability for the validation of space-borne atmospheric missions such as the TROPOspheric Monitoring Instrument (TROPOMI)/Sentinel-5 Precursor (S5P). We present the AROMAT campaigns from the perspective of findings related to the validation of tropospheric NO2, SO2, and H2CO. We also quantify the emissions of NOx and SO2 at both measurement sites. We show that tropospheric NO2 vertical column density (VCD) measurements using airborne mapping instruments are well suited for satellite validation in principle. The signal-to-noise ratio of the airborne NO2 measurements is an order of magnitude higher than its space-borne counterpart when the airborne measurements are averaged at the TROPOMI pixel scale. However, we show that the temporal variation of the NO2 VCDs during a flight might be a significant source of comparison error. Considering the random error of the TROPOMI tropospheric NO2 VCD (σ), the dynamic range of the NO2 VCDs field extends from detection limit up to 37 σ (2.6×1016 molec. cm−2) and 29 σ (2×1016 molec. cm−2) for Bucharest and the Jiu Valley, respectively. For both areas, we simulate validation exercises applied to the TROPOMI tropospheric NO2 product. These simulations indicate that a comparison error budget closely matching the TROPOMI optimal target accuracy of 25 % can be obtained by adding NO2 and aerosol profile information to the airborne mapping observations, which constrains the investigated accuracy to within 28 %. In addition to NO2, our study also addresses the measurements of SO2 emissions from power plants in the Jiu Valley and an urban hotspot of H2CO in the centre of Bucharest. For these two species, we conclude that the best validation strategy would consist of deploying ground-based measurement systems at well-identified locations.

The Airborne ROmanian Measurements of Aerosols and Trace gases (AROMAT) campaigns took place in Romania in September 2014 and August 2015. They focused on two sites: the Bucharest urban area and the power plants in the Jiu Valley. Their main objectives were to test recently developed airborne observation systems dedicated to air quality studies and to verify the concept of such campaigns in support of the validation of spaceborne atmospheric missions such as TROPOspheric Monitoring Instrument (TROPOMI)/Sentinel-5 Precursor (S5P). We show that tropospheric NO2 vertical column density (VCD) measurements using airborne mapping instruments are valuable for satellite validation. The signal to noise ratio of the airborne NO2 measurements is one order of magnitude higher than its spaceborne counterpart when the airborne measurements are averaged at the TROPOMI pixel scale. A significant source of comparison error appears to be the time variation of the NO2 VCDs during a flight, which we estimated at about 4 x 1015 molec cm-2 in the AROMAT conditions. Considering the random error of the TROPOMI tropospheric NO2 VCD (σ), the dynamic range of the NO2 VCDs field extends from detection limit up to 37σ (2.6 x 1016 molec cm-2) or 29σ (2 x 1016 molec cm-2) for Bucharest and the Jiu Valley, respectively. For the two areas, we simulate validation exercises of the TROPOMI tropospheric NO2 product using airborne measurements. These simulations indicate that we can closely approach the TROPOMI optimal target accuracy of 25 % by adding NO2 and aerosol profile information to the mapping data, which constrains the investigated accuracy within 28 %. In addition to NO2, we also measured significant amounts of SO2 in the Jiu Valley, as well as a hotspot of H2CO in the center of Bucharest. For these two species, we conclude that the best validation strategy would consist in deploying ground-based measurement systems at key locations which the AROMAT observations help identify.

North China (NC), namely Huabei in Chinese, is one of the most severely polluted regions in China, and the air pollution issues in this region have received a worldwide attention. We performed ground-based Multi Axis Differential Absorption Spectroscopy (MAX-DOAS) measurements at Gucheng, (39°08′N, 115°40′E), a rural site of North China about 110 km southwest of Beijing, from September 2008 to September 2010. The tropospheric vertical column densities (VCDs) of NO2 and SO2 were retrieved using the so-called geometric approximation. The results show that the tropospheric NO2 and SO2 VCDs over NC have nearly the same seasonal variation pattern, with the maximum in winter and minimum in summer, while their diurnal variations are different. We also compared the tropospheric NO2 and SO2 VCDs from our MAX-DOAS measurements with several products of corresponding OMI (Ozone Monitoring Instrument) satellite observations. While in summer good agreement is found, the satellite observations systematically underestimate the tropospheric NO2 in winter over the polluted rural area of NC, probably mostly due to the so called aerosol shielding effect. In contrast, for SO2 no such clear conclusion can be drawn, probably owing to the larger uncertainties from MAX-DOAS and in particular satellite retrievals. This indicates that improvements of the retrieval algorithm for MAX-DOAS and off-line corrections of satellite measurements for the tropospheric SO2 VCDs should be given more emphasis in the future.

In this study the consistency between MAX-DOAS measurements and radiative transfer simulations of the atmospheric O 4 absorption is investigated on two mainly clear days during the MAD-CAT campaign in Mainz, Germany, in Summer 2013. In recent years several studies indicated that measurements and radiative transfer simulations of the atmospheric O 4 absorption can only be brought into agreement if a so-called scaling factor ( 4 absorption. However, many studies, in particular based on direct sun light measurements, came to the opposite conclusion, that there is no need for a scaling factor. Up to now, there is no explanation for the observed discrepancies between measurements and simulations. Previous studies infered the need for a scaling factor from the comparison of the aerosol optical depth derived from MAX-DOAS O 4 measurements with that derived from coincident sun photometer measurements. In this study a different approach is chosen: the measured O 4 absorption at 360 nm is directly compared to the O 4 absorption obtained from radiative transfer simulations. The atmospheric conditions used as input for the radiative transfer simulations were taken from independent data sets, in particular from sun photometer and ceilometer measurements at the measurement site. The comparisons are performed for two selected clear days with similar aerosol optical depth but very different aerosol properties. For both days not only the O 4 absorptions are compared, but also all relevant error sources of the spectral analysis, the radiative transfer simulations as well as the extraction of the input parameters used for the radiative transfer simulations are quantified. One important result obtained from the analysis of synthetic spectra is that the O 4 absorptions derived from the spectral analysis agree within 1 % with the corresponding radiative transfer simulations. The performed tests and sensitivity studies might be useful for the analysis and interpretation of O 4 MAX-DOAS measurements in future studies. Different comparison results are found for both days: On 18 June, measurements and simulations agree within their (rather large) errors (the ratio of simulated and measured O 4 absorptions is found to be 1.01 ± 0.16). In contrast, on 8 July measurements and simulations significantly disagree: For the middle period of that day the ratio of simulated and measured O 4 absorptions is found to be 0.71 ± 0.12, which differs significantly from unity. Thus for that day a scaling factor is needed to bring measurements and simulations into agreement. One possible reason for the comparison results on 18 June is the rather large aerosol extinction (and its large uncertainty) close to the surface, which has a large effect on the radiative transfer simulations. Besides the inconsistent comparison results for both days, also no explanation for a O 4 scaling factor could be derived in this study. Thus similar, but more extended future studies should be performed, which preferably include more measurement days, more instruments and should be supported by more detailed independent aerosol measurements. Also additional wavelengths should be included. The MAX-DOAS measurements collected during the recent CINDI-2 campaign are probably well suited for that purpose.

Ground-based measurements of scattered sunlight by the Multi Axis Differential Optical Absorption Spectroscopy (MAX-DOAS) have been carried out at an urban site (39.95° N, 116.32° E) in Beijing megacity since 6 August 2008. In this study, we retrieved the tropospheric NO2 vertical column densities (VCDs) over Beijing from these MAX-DOAS observations from August 2008 to September 2011. Over this period, the daytime (08:00–17:00 Beijing Time (BJT, which equals UTC + 8)) mean tropospheric NO2 VCDs varied from 0.5 to 13.3 with an average of 3.6 during summertime, and from 0.2 to 16.8 with an average of 5.8 during wintertime, all in units of 1016 molecules cm−2. The average diurnal variation patterns of tropospheric NO2 over Beijing appeared to be rather different from one season to another, indicating differences in the emission strength and atmospheric lifetime. In contrast to previous studies, we find a small weekly cycle of the tropospheric NO2 VCD over Beijing. The NO2 VCD in the late afternoon was the largest on Saturday and the lowest on Sunday, and in the morning it reached a clear maximum on Wednesday. We also find a post-Olympic Games effect, with 39–54% decrease in the tropospheric NO2 VCD over Beijing estimated for August of 2008, compared to the following years. The tropospheric NO2 VCDs derived by our ground MAX-DOAS measurements show a good correlation with SCIAMACHY and OMI satellite data. However, compared with the MAX-DOAS measurements, the satellite observations underestimate the tropospheric NO2 VCDs over Beijing systematically, by 43% for SCIAMACHY and 26–38% for OMI (DOMINO v2.0 and DOMINO v1.02). Based on radiative transfer simulations, we show that the aerosol shielding effect can explain this underestimation, while the gradient smoothing effect caused by the coarse spatial resolution of the satellite observations could play an additional role.

We present intercomparison results for formaldehyde (HCHO) slant column measurements performed during the Cabauw Intercomparison campaign of Nitrogen Dioxide measuring Instruments (CINDI) that took place in Cabauw, the Netherlands, in summer 2009. During two months, nine atmospheric research groups simultaneously operated MAX-DOAS (MultiAXis Differential Optical Absorption Spectroscopy) instruments of various designs to record UV-visible spectra of scattered sunlight at different elevation angles that were analysed using common retrieval settings. The resulting HCHO data set was found to be highly consistent, the mean difference between instruments generally not exceeding 15% or 7.5 × 1015 molec cm−2, for all viewing elevation angles. Furthermore, a sensitivity analysis was performed to investigate the uncertainties in the HCHO slant column retrieval when varying key input parameters such as the molecular absorption cross sections, correction terms for the Ring effect or the width and position of the fitting interval. This study led to the identification of potentially important sources of errors associated with cross-correlation effects involving the Ring effect, O4, HCHO and BrO cross sections and the DOAS closure polynomial. As a result, a set of updated recommendations was formulated for HCHO slant column retrieval in the 336.5–359 nm wavelength range. To conclude, an error budget is proposed which distinguishes between systematic and random uncertainties. The total systematic error is estimated to be of the order of 20% and is dominated by uncertainties in absorption cross sections and related spectral cross-correlation effects. For a typical integration time of one minute, random uncertainties range between 5 and 30%, depending on the noise level of individual instruments.

In this study we report on airborne imaging DOAS measurements of NO2 from two flights performed in Bucharest during the AROMAT campaign (Airborne ROmanian Meeasurements of Aerosols an 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 NO2 below the aircraft with a high spatial resolution of better than 100 m. The airmass 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 measured intensities at the aircraft. 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 seen in the NO2 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 NO2 across the city. Pollution levels range from background values in the outskirts located upwind of the city to about 4 × 1016 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 cofficients of R = 0.94 and R = 0.85, respectively. Estimations on the NOx emission rate of Bucharest for the two flights yield emission rates of 15.1 ± 9.4 mol s−1 and 13.6 ± 8.4 mol s−1, respectively.

Standard methods like in-situ measurements can hardly register NOx (= NO + NO2) emissions from aircrafts during take-off, when engines run at high load and thus an important amount of fuel is consumed and most of the harmful emissions are produced . The goal of this work is to show that it is possible to measure aircraft emissions generated during take-off (and initial part of the climb) by a remote spectroscopic method like automobile – based – Differential Optical Absorption Spectroscopy (Mobile-DOAS), which uses scattered solar radiation in the blue spectral range (around 445 nm). In order to test its feasibility, total column measurements of NO2 encircling Frankfurt Airport were carried out on 23 February 2012 using Mobile-DOAS. Also, NOx fluxes were derived from the NO2 observations. Unlike standard mobile-DOAS measures using a spectrometer looking at zenith, the measurements were performed looking at 22° elevation angle leading to a roughly two to three times higher sensitivity compared to zenith observations. The origin of the observed NO2 is discussed and the total NOx fluxes are calculated. As result of three round-trips encircling the Frankfurt Airport, the mean NOx flux was found to correlate with the number of aircrafts taking-off. Our results demonstrate that mobile-DOAS method is suitable for quantifying emissions from airports and to study their impact in the planetary boundary layer, which is most relevant concerning the impact on the environment and the human health.

A method is developed for the calibration of the colour index (CI) and the O4 absorption derived from Differential Optical Absorption Spectroscopy (DOAS) measurements of scattered sunlight. The method is based on the comparison of measurements and radiative transfer simulations for well-defined atmospheric conditions and viewing geometries. Calibrated measurements of the CI and the O4 absorption are important for the detection and classification of clouds from MAX-DOAS observations. Such information is needed for the identification and correction of the cloud influence on Multi-AXis (MAX-) DOAS profile inversion results, but might be also be of interest on their own, e.g. for meteorological applications. The calibration algorithm was successfully applied to measurements at two locations: Cabauw in the Netherlands and Wuxi in China. We used CI and O4 observations calibrated by the new method as input to our recently developed cloud classification scheme and adapted also the corresponding threshold values accordingly. For the observations at Cabauw good agreement is found with the results of the original algorithm. Together with the calibration procedure of the CI and O4 absorption the cloud classification scheme, which was tuned to specific locations/conditions so far, can now be applied consistently to MAX-DOAS measurements at different locations. In addition to the new threshold values, further improvements were introduced to the cloud classification algorithm, namely a better description of the SZA dependence of the threshold values and a new set of wavelengths for the determination of the CI. We also indicate specific areas for future research to further improve the cloud classification scheme.

In June 2009, 22 spectrometers from 14 institutes measured tropospheric and stratospheric NO2 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 non-zenith 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 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 NO2 and O4 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 NO2, as previous intercomparisons were only for zenith instruments focussing on stratospheric NO2, with their longer heritage.

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 extinction 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. AOTs 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.

This paper discusses the findings of the first car MAX-DOAS (multi-axis differential optical absorption spectroscopy) field campaign (300km long) along the National Highway-05 (N5-Highway) of Pakistan conducted on 13 and 14 November, 2012. The main objective of the field campaign was to assess the spatial distribution of tropospheric nitrogen dioxide (NO2) columns and corresponding concentrations along the N5-Highway from Islamabad to Lahore. Source identification of NO2 revealed that the concentrations were higher within major cities along the highway. The highest NO2 vertical column densities (NO2 VCDs) were found around two major cities of Rawalpindi and Lahore. This study also presents a comparison of NO2 VCDs measured by the ozone monitoring instrument (OMI) and car MAX-DOAS observations. The comparison revealed similar spatial distribution of the NO2 columns with both car MAX-DOAS and satellite observations, but the car MAX-DOAS observations show much more spatial details. Maximum NO2 VCD retrieved from car MAX-DOAS observations was up to an order of magnitude larger than the OMI observations in urban areas.

From June to July 2009 more than thirty different in-situ and remote sensing instruments from all over the world participated in the Cabauw Intercomparison campaign for Nitrogen Dioxide measuring Instruments (CINDI). The campaign took place at KNMI's Cabauw Experimental Site for Atmospheric Research (CESAR) in the Netherlands. Its main objectives were to determine the accuracy of state-of-the-art ground-based measurement techniques for the detection of atmospheric nitrogen dioxide (both in-situ and remote sensing), and to investigate their usability in satellite data validation. The expected outcomes are recommendations regarding the operation and calibration of such instruments, retrieval settings, and observation strategies for the use in ground-based networks for air quality monitoring and satellite data validation. Twenty-four optical spectrometers participated in the campaign, of which twenty-one had the capability to scan different elevation angles consecutively, the so-called Multi-axis DOAS systems, thereby collecting vertical profile information, in particular for nitrogen dioxide and aerosol. Various in-situ samplers and lidar instruments simultaneously characterized the variability of atmospheric trace gases and the physical properties of aerosol particles. A large data set of continuous measurements of these atmospheric constituents has been collected under various meteorological conditions and air pollution levels. Together with the permanent measurement capability at the CESAR site characterizing the meteorological state of the atmosphere, the CINDI campaign provided a comprehensive observational data set of atmospheric constituents in a highly polluted region of the world during summertime. First detailed comparisons performed with the CINDI data show that slant column measurements of NO2, O4 and HCHO with MAX-DOAS agree within 5 to 15%, vertical profiles of NO2 derived from several independent instruments agree within 25% of one another, and MAX-DOAS aerosol optical thickness agrees within 20–30% with AERONET data. For the in-situ NO2 instrument using a molybdenum converter, a bias was found as large as 5 ppbv during day time, when compared to the other in-situ instruments using photolytic converters.

In the field, aerosol in-situ measurements are often performed under dry conditions (relative humidity RHsp(λ) was measured dry and at various, predefined RH conditions between 20 and 95% with a humidified nephelometer. The scattering enhancement factor f(RH,λ) is the key parameter to describe the effect of RH on σsp(λ) and is defined as σsp(RH,λ) measured at a certain RH divided by the dry σsp(dry,λ). The measurement of f(RH,λ) together with the dry absorption measurement (assumed not to change with RH) allows the determination of the actual extinction coefficient σep(RH,λ) at ambient RH. In addition, a wide range of other aerosol properties were measured in parallel. The measurements were used to characterize the effects of RH on the aerosol optical properties. A closure study showed the consistency of the aerosol in-situ measurements. Due to the large variability of air mass origin (and thus aerosol composition) a simple parameterization of f(RH,λ) could not be established. If f(RH,λ) needs to be predicted, the chemical composition and size distribution need to be known. Measurements of four MAX-DOAS (multi-axis differential optical absorption spectroscopy) instruments were used to retrieve vertical profiles of σep(λ). The values of the lowest layer were compared to the in-situ values after conversion of the latter ones to ambient RH. The comparison showed a good correlation of R2 = 0.62–0.78, but the extinction coefficients from MAX-DOAS were a factor of 1.5–3.4 larger than the in-situ values. Best agreement is achieved for a few cases characterized by low aerosol optical depths and low planetary boundary layer heights. Differences were shown to be dependent on the applied MAX-DOAS retrieval algorithm. The comparison of the in-situ extinction data to a Raman LIDAR (light detection and ranging) showed a good correlation and higher values measured by the LIDAR (R2 = 0.82−0.85, slope of 1.69–1.76) if the Raman retrieved profile was used to extrapolate the directly measured extinction coefficient to the ground. The comparison improved if only nighttime measurements were used in the comparison (R2 = 0.96, slope of 1.12).