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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.

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 () is applied to the measured O4 absorption. However, many studies, including those based on direct sunlight measurements, came to the opposite conclusion, that there is no need for a scaling factor. Up to now, there is no broad consensus for an explanation of the observed discrepancies between measurements and simulations. Previous studies inferred the need for a scaling factor from the comparison of the aerosol optical depths derived from MAX-DOAS O4 measurements with that derived from coincident sun photometer measurements. In this study a different approach is chosen: the measured O4 absorption at 360 nm is directly compared to the O4 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. This study has three main goals: first all relevant error sources of the spectral analysis, the radiative transfer simulations and 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 O4 absorptions derived from the spectral analysis agree within 1 % with the corresponding radiative transfer simulations at 360 nm. Based on the results from sensitivity studies, recommendations for optimised settings for the spectral analysis and radiative transfer simulations are given. Second, the measured and simulated results are compared for 2 selected cloud-free days with similar aerosol optical depths but very different aerosol properties. On 18 June, measurements and simulations agree within their (rather large) uncertainties (the ratio of simulated and measured O4 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 O4 absorptions is found to be 0.82±0.10, which differs significantly from unity. Thus, for that day a scaling factor is needed to bring measurements and simulations into agreement. Third, recommendations for further intercomparison exercises are derived. One important recommendation for future studies is that aerosol profile data should be measured at the same wavelengths as the MAX-DOAS measurements. Also, the altitude range without profile information close to the ground should be minimised and detailed information on the aerosol optical and/or microphysical properties should be collected and used. The results for both days are inconsistent, and no explanation for a O4 scaling factor could be derived in this study. Thus, similar but more extended future studies should be performed, including more measurement days and more instruments. Also, additional wavelengths should be included.

We determined NOx emissions from Paris in summer 2009 and winter 2009/2010 by applying the closed integral method (CIM) to a large set of car multi-axis differential optical absorption spectroscopy (MAX-DOAS) measurements performed within the framework of the MEGAPOLI project (http://megapoli.dmi.dk/). MAX-DOAS measurements of the tropospheric NO2 vertical column density (VCD) were performed in large circles around Paris. From the combination of the observed NO2 VCDs with wind fields, the NO2 influx into and the outflux from the encircled area was determined. The difference between the influx and outflux represents the total emission. Compared to previous applications of the CIM, the large number of measurements during the MEGAPOLI campaign allowed the investigation of important aspects of the CIM. In particular, the applicability of the CIM under various atmospheric conditions could be tested. Another important advantage of the measurements during MEGAPOLI is that simultaneous atmospheric model simulations with a high spatial resolution (3 × 3 km2) are available for all days. Based on these model data, it was possible to test the consistency of the CIM and to derive information about favourable or non-favourable conditions for the application of the CIM. We found that in most situations the uncertainties and the variability in the wind data dominate the total error budget, which typically ranges between 30 and 50 %. Also, measurement gaps and uncertainties in the partitioning ratio between NO and NO2 are important error sources. Based on a consistency check, we deduced a set of criteria on whether measurement conditions are suitable or not for the application of the CIM. We also developed a method for the calculation of the total error budget of the derived NOx emissions. Typical errors are between ±30 and ±50 % for individual days (with one full circle around Paris). From the application of the CIM to car MAX-DOAS observations we derive daily average NOx emissions for Paris of 4.0 × 1025 molec s−1 for summer and of 6.9 × 1025 molec s−1 in winter. These values are a factor of about 1.4 and 2.0 larger than the corresponding emissions derived from the application of the CIM to the model data, using the Toegepast Natuurwetenschappelijk Onderzoek (TNO) MEGAPOLI emission inventory, in summer and winter, respectively. Similar ratios (1.5 and 2.3 for summer and winter, respectively) were found for the comparison with the Monitoring Atmospheric composition and climate III (MACC-III) emission inventory. The highest NOx emissions were found during some cold days in February. Enhanced domestic heating and a reduced conversion efficiency of catalytic converters might contribute to these enhanced NOx emissions.

In this study we report on airborne imaging DOAS measurements of NO2 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 NO2 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 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 coefficients 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 and 13.6 ± 8.4 mol s−1, respectively.

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 for our recently developed cloud classification scheme and also adapted 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 has been 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 (solar zenith angle) 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.

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.

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 shortwave 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, 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 < 7 %. For wavelengths below about 330 nm it is essential that the ozone column density during the measurements be constant and known.

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 spatiotemporal 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 vertical column densities (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.

Multi-axis differential optical absorption spectroscopy (MAX-DOAS) observations of aerosols and trace gases can be strongly influenced by clouds. Thus, it is important to identify clouds and characterise their properties. In this study we investigate the effects of clouds on several quantities which can be derived from MAX-DOAS observations, like radiance, the colour index (radiance ratio at two selected wavelengths), the absorption of the oxygen dimer O4 and the fraction of inelastically scattered light (Ring effect). To identify clouds, these quantities can be either compared to their corresponding clear-sky reference values, or their dependencies on time or viewing direction can be analysed. From the investigation of the temporal variability the influence of clouds can be identified even for individual measurements. Based on our investigations we developed a cloud classification scheme, which can be applied in a flexible way to MAX-DOAS or zenith DOAS observations: in its simplest version, zenith observations of the colour index are used to identify the presence of clouds (or high aerosol load). In more sophisticated versions, other quantities and viewing directions are also considered, which allows subclassifications like, e.g., thin or thick clouds, or fog. We applied our cloud classification scheme to MAX-DOAS observations during the Cabauw intercomparison campaign of Nitrogen Dioxide measuring instruments (CINDI) campaign in the Netherlands in summer 2009 and found very good agreement with sky images taken from the ground and backscatter profiles from a lidar.

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.

We developed an algorithm for the retrieval of the atmospheric water vapour column from Multi-AXis Differential Optical Absorption Spectroscopy (MAX-DOAS) observations in the yellow and red spectral range. The retrieval is based on the so-called geometric approximation and does not depend on explicit a priori information for individual observations, extensive radiative transfer simulations, or the construction of large look-up tables. Disturbances of the radiative transfer due to aerosols and clouds are simply corrected using the simultaneously measured absorptions of the oxygen dimer, O4. We applied our algorithm to MAX-DOAS observations made at the Max Planck Institute for Chemistry in Mainz, Germany, from March to August 2011, and compared the results to independent observations. Good agreement with Aerosol Robotic Network (AERONET) and European Centre for Medium-Range Weather Forecasting (ECMWF) H2O vertical column densities (VCDs) is found, while the agreement with satellite observations is less good, most probably caused by the shielding effect of clouds for the satellite observations. Good agreement is also found with near-surface in situ observations, and it was possible to derive average daily H2O scale heights (between 1.5 km and 3 km). MAX-DOAS measurements use cheap and simple instrumentation and can be run automatically. One important advantage of our algorithm is that the H2O VCD can be retrieved even under cloudy conditions (except clouds with very high optical thickness).

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.

We present the first Multi-Axis-(MAX-) DOAS observations in India performed during April 2010 and January 2011 in Delhi and nearby regions. The MAX-DOAS instrument was mounted on a car roof, which allowed us to perform measurements along individual driving routes. From car MAX-DOAS observations along closed circles around Delhi, together with information on wind speed and direction, the NOx emissions from the greater Delhi area were determined: our estimate of 4.4 × 1025 molecules s−1 is found to be slightly lower than the corresponding emission estimates using the EDGAR emission inventory and substantially smaller compared to a recent study by Gurjar et al. (2004). We also determined NOx emissions from Delhi using OMI satellite observations on the same days. These emissions are slightly smaller than those from the car MAX-DOAS measurements. Finally the car MAX-DOAS observations were also used for the validation of simultaneous OMI satellite measurements of the tropospheric NO2 VCD and found a good agreement of the spatial patterns. Concerning the absolute values, OMI data are, on average, higher than the car MAX-DOAS observations close to strong emission sources, and vice versa over less polluted regions. Our results indicate that OMI NO2 VCDs are biased low over strongly polluted regions, probably caused by inadequate a-priori profiles used in the OMI satellite retrieval.

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).

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.

We present car Multi-Axis (MAX-) DOAS observations of tropospheric NO2 carried out on circles around the cities of Mannheim and Ludwigshafen (Germany) on 24 August 2006. Together with information on wind speed and direction, the total emissions of the encircled source(s) are quantified from these measurements. In contrast to recent similar studies based on zenith scattered sun light (elevation angle of 90°), we use a MAX-DOAS instrument mounted on a car, which observes scattered sun light under different elevation angles (here 45°, and 90°). Compared to simple zenith sky observations, MAX-DOAS observations have higher sensitivity and reduced uncertainty, and avoid systematic offsets in the determination of the vertically integrated trace gas concentration. The determination of the absolute value of the integrated tropospheric trace gas concentrations is especially important for the calculation of absolute trace gas fluxes through arbitrary transects. However, even if emission sources are completely surrounded, systematic offsets in the measured vertically integrated trace gas concentration can lead to errors in the determined total emissions, especially for observations around extended areas. In this study we discuss and quantify different error sources. In most cases, the largest error source is the variability and imperfect knowledge of the wind field. In addition – depending on the trace species observed - also chemical transformations between the emission sources and the measurement location have to be considered. For that purpose we use local observations within the encircled area to quantify and/or correct these errors. From our observations we derive a total NOx emission from the Mannheim/Ludwigshafen area of (7.4±1.8)×1024 molec/sec, which if assumed to be constant throughout the year would correspond to a total emission of 17 830±4340 t/yr (calculated with the mass of NO2 t/yr, consistent with existing emission estimates. From our observations it is also possible to separately determine the average influx into the Mannheim/Ludwigshafen area (5.4±0.9×1024 molec/sec or 13 010±2170 t/yr) and the average outflux (12.8±1.8×1024 molec/sec or 13 010±4340 t/yr).

From Multi-Axis- (MAX-) DOAS observations, information on tropospheric trace gases close to the surface and up to the free troposphere can be obtained. Usually MAX-DOAS observations are performed at fixed locations, which allows to retrieve the diurnal variation of tropospheric species at that location. Alternatively, MAX-DOAS observations can also be made on mobile platforms like cars, ships or aircrafts. Then, in addition to the vertical (and temporal) distribution, also the horizontal variation of tropospheric trace gases can be measured. Such information is important for the quantitative comparison with model simulations, study of transport processes, and for the validation of tropospheric trace gas products from satellite observations. However, for MAX-DOAS observations from mobile platforms, the standard analysis techniques for MAX-DOAS observations can usually not be applied, because the probed airmasses can change rapidly between successive measurements. In this study we introduce a new technique which overcomes these problems and allows the exploitation of the full information content of mobile MAX-DOAS observations. Our method can also be applied to MAX-DOAS observations made at fixed locations in order to improve the accuracy especially in cases of strong winds. We apply the new technique to MAX-DOAS observations made during an automobile trip from Brussels to Heidelberg.

No abstract available.

No abstract available.

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., (Copyright © 2015. Published by Elsevier B.V.)