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In this paper we present a new method for retrieving tropospheric NO2 Vertical Column Density (VCD) from zenith-sky Differential Optical Absorption Spectroscopy (DOAS) measurements using mobile observations. This method was used during three days in the summer of 2011 in Romania, being to our knowledge the first mobile DOAS measurements peformed in this country. The measurements were carried out over large and different areas using a mobile DOAS system installed in a car. We present here a step-by-step retrieval of tropospheric VCD using complementary observations from ground and space which take into account the stratospheric contribution, which is a step forward compared to other similar studies. The detailed error budget indicates that the typical uncertainty on the retrieved NO2tropospheric VCD is less than 25%. The resulting ground-based data set is compared to satellite measurements from the Ozone Monitoring Instrument (OMI) and the Global Ozone Monitoring Experiment-2 (GOME-2). For instance, on 18 July 2011, in an industrial area located at 47.03°N, 22.45°E, GOME-2 observes a tropospheric VCD value of (3.4 ± 1.9) × 1015 molec./cm2, while average mobile measurements in the same area give a value of (3.4 ± 0.7) × 10(15) molec./cm2. On 22 August 2011, around Ploiesti city (44.99°N, 26.1°E), the tropospheric VCD observed by satellites is (3.3 ± 1.9) × 10(15) molec./cm2 (GOME-2) and (3.2 ± 3.2) × 10(15) molec./cm2 (OMI), while average mobile measurements give (3.8 ± 0.8) × 10(15) molec./cm2. Average ground measurements over "clean areas", on 18 July 2011, give (2.5 ± 0.6) × 10(15) molec./cm2 while the satellite observes a value of (1.8 ± 1.3) × 10(15) molec./cm2.

We present an algorithm for retrieving tropospheric nitrogen dioxide (NO2) vertical column densities (VCDs) from ground-based zenith-sky (ZS) measurements of scattered sunlight. The method is based on a four-step approach consisting of (1) the differential optical absorption spectroscopy (DOAS) analysis of ZS radiance spectra using a fixed reference spectrum corresponding to low NO2 absorption, (2) the determination of the residual amount in the reference spectrum using a Langley-plot-type method, (3) the removal of the stratospheric content from the daytime total measured slant column based on stratospheric VCDs measured at sunrise and sunset, and simulation of the rapid NO2 diurnal variation, (4) the retrieval of tropospheric VCDs by dividing the resulting tropospheric slant columns by appropriate air mass factors (AMFs). These steps are fully characterized and recommendations are given for each of them. The retrieval algorithm is applied on a ZS data set acquired with a multi-axis (MAX-) DOAS instrument during the Cabauw (51.97° N, 4.93° E, sea level) Intercomparison campaign for Nitrogen Dioxide measuring Instruments (CINDI) held from 10 June to 21 July 2009 in the Netherlands. A median value of 7.9 × 1015 molec cm-2 is found for the retrieved tropospheric NO2 VCDs, with maxima up to 6.0 × 1016 molec cm-2. The error budget assessment indicates that the overall error σTVCD on the column values is less than 28 %. In the case of low tropospheric contribution, σTVCD is estimated to be around 39% and is dominated by uncertainties in the determination of the residual amount in the reference spectrum. For strong tropospheric pollution events, σTVCD drops to approximately 22% with the largest uncertainties on the determination of the stratospheric NO2 abundance and tropospheric AMFs. The tropospheric VCD amounts derived from ZS observations are compared to VCDs retrieved from off-axis and direct-sun measurements of the same MAX-DOAS instrument as well as to data from a co-located Système d'Analyse par Observations Zénithales (SAOZ) spectrometer. The retrieved tropospheric VCDs are in good agreement with the different data sets with correlation coefficients and slopes close to or larger than 0.9. The potential of the presented ZS retrieval algorithm is further demonstrated by its successful application on a 2-year data set, acquired at the NDACC (Network for the Detection of Atmospheric Composition Change) station Observatoire de Haute Provence (OHP; Southern France). [ABSTRACT FROM AUTHOR]

A 4-year data set of MAX-DOAS observations in the Beijing area (2008–2012) is analysed with a focus on NO2, HCHO and aerosols. Two very different retrieval methods are applied. Method A describes the tropospheric profile with 13 layers and makes use of the optimal estimation method. Method B uses 2–4 parameters to describe the tropospheric profile and an inversion based on a leastsquares fit. For each constituent (NO2, HCHO and aerosols) the retrieval outcomes are compared in terms of tropospheric column densities, surface concentrations and "characteristic profile heights" (i.e. the height below which 75% of the vertically integrated tropospheric column density resides). We find best agreement between the two methods for tropospheric NO2 column densities, with a standard deviation of relative differences below 10 %, a correlation of 0.99 and a linear regression with a slope of 1.03. For tropospheric HCHO column densities we find a similar slope, but also a systematic bias of almost 10% which is likely related to differences in profile height. Aerosol optical depths (AODs) retrieved with method B are 20% high compared to method A. They are more in agreement with AERONET measurements, which are on average only 5% lower, however with considerable relative differences (standard deviation ~25 %). With respect to near-surface volume mixing ratios and aerosol extinction we find considerably larger relative differences: 10±30, –23±28 and –8±33% for aerosols, HCHO and NO2 respectively. The frequency distributions of these near-surface concentrations show however a quite good agreement, and this indicates that near-surface concentrations derived from MAX-DOAS are certainly useful in a climatological sense. A major difference between the two methods is the dynamic range of retrieved characteristic profile heights which is larger for method B than for method A. This effect is most pronounced for HCHO, where retrieved profile shapes with method A are very close to the a priori, and moderate for NO2 and aerosol extinction which on average show quite good agreement for characteristic profile heights below 1.5 km. One of the main advantages of method A is the stability, even under suboptimal conditions (e.g. in the presence of clouds). Method B is generally more unstable and this explains probably a substantial part of the quite large relative differences between the two methods. However, despite a relatively low precision for individual profile retrievals it appears as if seasonally averaged profile heights retrieved with method B are less biased towards a priori assumptions than those retrieved with method A. This gives confidence in the result obtained with method B, namely that aerosol extinction profiles tend on average to be higher than NO2 profiles in spring and summer, whereas they seem on average to be of the same height in winter, a result which is especially relevant in relation to the validation of satellite retrievals. [ABSTRACT FROM AUTHOR]

A four year data set of MAX-DOAS observations in the Beijing area (2008-2012) is analysed with a focus on NO2, HCHO, and aerosols. Two very different retrieval methods are applied. Method A describes the tropospheric profile with 13 layers and makes use of the optimal estimation method. Method B uses 2-4 parameters to describe the tropospheric profile and an inversion based on a least-squares fit. For each constituent (NO2, HCHO and aerosols) the retrieval outcomes are compared in terms of tropospheric columns, surface concentrations, and "characteristic profile heights" (i.e. the height below which 75% of the vertically integrated tropospheric column resides). We find best agreement between the two methods for tropospheric NO2 columns, with a standard deviation of relative differences below 10%, a correlation of 0.99 and a linear regression with a slope of 1.03. For tropospheric HCHO columns we find a similar slope, but also a systematic bias of almost 10 % which is likely related to differences in profile height. Aerosol optical depths (AODs) retrieved with method B are 20% high compared to method A. They are more in agreement with AERONET measurements, which are on average only 5% lower, however with considerable relative differences (standard deviation ~ 25%). With respect to near surface volume mixing ratios and aerosol extinction we find considerably larger relative differences: 10 ± 30%, -23 ± 28% and - 8 ± 33% for aerosols, HCHO and NO2 respectively. The frequency distributions of these near-surface concentrations show however a quite good agreement, and this indicates that near-surface concentrations derived from MAX-DOAS are certainly useful in a climatological sense. A major difference between the two methods is the dynamic range of retrieved characteristic profile heights which is larger for method B than for method A. This effect is most pronounced for HCHO, where retrieved profile shapes with method A are very close to the a priori, and moderate for NO2 and aerosols which on average show quite good agreement for characteristic profile heights below 1.5 km. [ABSTRACT FROM AUTHOR]

Ground-based Multi-Axis Differential Optical Absorption Spectroscopy (MAX-DOAS) measurements of nitrous acid (HONO) and its precursor NO2 (nitrogen dioxide) as well as aerosols have been performed daily in Beijing city centre (39.98° N, 116.38° E) from July 2008 to April 2009 and at the suburban site of Xianghe (39.75° N, 116.96° E) located ~60 km east of Beijing from March 2010 to December 2012. This extensive dataset allowed for the first time the investigation of the seasonal cycle of HONO as well as its diurnal variation in and in the vicinity of a megacity. Our study was focused on the HONO and NO2 near-surface concentrations (0-200m layer) and total vertical column densities (VCDs) and also aerosol optical depths (AODs) and extinction coefficients retrieved by applying the Optimal Estimation Method to the MAX-DOAS observations. Monthly averaged HONO near-surface concentrations at local noon display a strong seasonal cycle with a maximum in late fall/winter (~0.8 and 0.7 ppb at Beijing and Xianghe, respectively) and a minimum in summer (~0.1 ppb at Beijing and 0.03 ppb at Xianghe). The seasonal cycles of HONO and NO2 appear to be highly correlated, with correlation coefficients in the 0.7-0.9 and 0.5-0.8 ranges at Beijing and Xianghe, respectively. The stronger correlation of HONO with NO2 and also with aerosols observed in Beijing suggests possibly larger role of NO2 conversion into HONO in the Beijing city center than at Xianghe. The observed diurnal cycle of HONO near-surface concentration shows a maximum in the early morning (about 1 ppb at both sites) likely resulting from night-time accumulation, followed by a decrease to values of about 0.1-0.4 ppb around local noon. The HONO/NO2 ratio shows a similar pattern with a maximum in the early morning (values up to 0.08) and a decrease to ~0.01-0.02 around local noon. The seasonal and diurnal cycles of the HONO near-surface concentration are found to be similar in shape and in relative amplitude to the corresponding cycles of the HONO total VCD and are therefore likely driven mainly by the balance between HONO sources and the photolytic sink, whereas dilution effects appear to play only a minor role. The estimation of OH radical production from HONO and O3 photolysis based on retrieved HONO near-surface concentrations and calculated photolysis rates indicate that in the 0-200m altitude range, HONO is by far the largest source of OH radicals in winter as well as in the early morning at all seasons, while the contribution of O3 dominates in summer from mid-morning until mid-afternoon. [ABSTRACT FROM AUTHOR]

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 MAXDOAS (MultiAXis Differential Optical Absorption Spectroscopy) instruments of various designs to record UVvisible 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 crosscorrelation 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. [ABSTRACT FROM AUTHOR]

The article discusses the use of Multi-AXis differential optical absorption spectroscopy (DOAS) (MAXDOAS) technique for formaldehyde (HCHO) slant column measurements during the 2009 Cabauw Intercomparison Campaign of Nitrogen Dioxide measuring Instruments (CINDI) in the Netherlands. Sensitivity analysis was performed to examine the uncertainties in slant column. It mentions that recommendation was developed for HCHO slant column retrieval in the 336.5-359 nanometer (nm) wavelenght range.

The article presents the algorithm for the retrieval of total and tropospheric NO2 columns from the Global Ozone Monitoring Experiment (GOME-2). The slant columns are determined through the Differential Optical Absorption Spectroscopy (DOAS) method. They are found to be in good overall agreement with ground-based measurements at the Observatoire de Haute Provence (OHP) in France. Uncertainties associated with the computation of the tropospheric air mass factor are also noted.