Tropospheric NO2 Vertical Column Densities Research Articles

Spatio-temporal Distributions of Tropospheric NO2 over oases in Taklimakan Desert, China

Soil biogenic NO emission is one of the most important sources of atmospheric nitrogen oxides (NOx) worldwide. However, the estimation of soil source, especially in arid areas presents large uncertainties because of the substantial lack of measurements. In this study, we selected the Ruoqiang oases on the southeastern edge of the Taklimakan Desert, China as the study area and applied Ozone Monitoring Instrument (OMI) NO2 retrievals (DOMINO v2.0, 2005–2011) to investigate the spatial distribution and seasonal variations in tropospheric NO2 vertical column density (VCD). High NO2 VCDs were observed over the oases (farmlands and natural vegetation), with the highest value obtained during summer, and lowest during winter. Pulses were observed during spring. We conducted in-situ measurements in June 2011 in Milan oasis and employed ground-based multi-axis differential optical absorption spectroscopy (MAX-DOAS) instruments to validate satellite NO2 retrievals. The findings are as follows: 1) in the study area soil biogenic NO emission is the dominant source of tropospheric NO2; 2) oases (farmlands) are hotspots of tropospheric NO2, and a higher increase in tropospheric NO2 is found in oases from winter to summer; and 3) enhancement of soil biogenic NO emission due to soil managements is predictable. Given the rapid agricultural development in the southern Uygur Autonomous Region of Xinjiang, researches on soil biogenic NO emission and increase in tropospheric NOx should be given more importance.

Regional modeling of tropospheric NO<sub>2</sub> vertical column density over East Asia during the period 2000–2010: comparison with multisatellite observations

Abstract. Satellite observations of the tropospheric NO2 vertical column density (VCD) are closely correlated to, and thus can be used to estimate, surface NOx emissions. In this study, the NO2 VCD simulated by a regional chemical transport model with emissions data from the updated Regional Emission inventory in ASia (REAS) version 2.1 were validated through comparison with multisatellite observations during the period 2000–2010. Rapid growth in NO2 VCD (~11% year−1) driven by the expansion of anthropogenic NOx emissions was identified above the central eastern China (CEC) region, except for the period during the economic downturn. In contrast, slightly decreasing trends (~2% year−1) were identified above Japan accompanied by a decline in anthropogenic emissions. To systematically compare the modeled NO2 VCD, we estimated sampling bias and the effect of applying the averaging kernel information, with particular focus on the SCanning Imaging Absorption spectroMeter for Atmospheric CHartographY (SCIAMACHY) data. Using the updated REAS, the modeled NO2 VCD reasonably reproduced annual trends observed by multisatellites, suggesting that the rate of increase of NOx emissions estimated by the updated REAS inventory would be robust. Province-scale revision of emissions above CEC is needed to further refine emission inventories. Based on the close linear relationship between modeled and observed NO2 VCD and anthropogenic NOx emissions, NOx emissions in 2009 and 2010, which were not covered by the updated REAS inventory, were estimated. NOx emissions from anthropogenic sources in China in 2009 and 2010 were determined to be 26.4 and 28.5 Tg year−1, respectively, indicating that NOx emissions increased more than twofold between 2000 and 2010. This increase reflected the strong growth of anthropogenic emissions in China following the rapid recovery from the economic downturn from late 2008 until mid-2009. Our method consists of simple estimations from satellite observations and provides results that are consistent with the most recent inventory of emissions data for China.

Comparison of tropospheric NO<sub>2</sub> vertical columns in an urban environment using satellite, multi-axis differential optical absorption spectroscopy, and in situ measurements

Abstract. Tropospheric NO2 vertical column densities have been retrieved and compared for the first time in Toronto, Canada, using three methods of differing spatial scales. Remotely sensed NO2 vertical column densities, retrieved from multi-axis differential optical absorption spectroscopy and satellite remote sensing, were evaluated by comparison with in situ vertical column densities estimated using a pair of chemiluminescence monitors situated 0.01 and 0.5 km a.g.l. (above ground level). The chemiluminescence measurements were corrected for the influence of NOz, which reduced the NO2 concentrations at 0.01 and 0.5 km by an average of 8 ± 1% and 12 ± 1%, respectively. The average absolute decrease in the chemiluminescence NO2 measurement as a result of this correction was less than 1 ppb. The monthly averaged ratio of the NO2 concentration at 0.5 to 0.01 km varied seasonally, and exhibited a negative linear dependence on the monthly average temperature, with Pearson's R = 0.83. During the coldest month, February, this ratio was 0.52 ± 0.04, while during the warmest month, July, this ratio was 0.34 ± 0.04, illustrating that NO2 is not well mixed within 0.5 km above ground level. Good correlation was observed between the remotely sensed and in situ NO2 vertical column densities (Pearson's R value ranging from 0.72 to 0.81), but the in situ vertical column densities were 52 to 58% greater than the remotely sensed columns. These results indicate that NO2 horizontal heterogeneity strongly impacted the magnitude of the remotely sensed columns. The in situ columns reflected an urban environment with major traffic sources, while the remotely sensed NO2 vertical column densities were representative of the region, which included spatial heterogeneity introduced by residential neighbourhoods and Lake Ontario. Despite the difference in absolute values, the reasonable correlation between the vertical column densities determined by three distinct methods increased confidence in the validity of the values provided by each measurement technique.

Simulated air quality and pollutant budgets over Europe in 2008

Major gaseous and particulate pollutant levels over Europe in 2008 have been simulated using the offline-coupled WRFCMAQ chemistry and transport modeling system. The simulations are compared with surface observations from the EMEP stations, ozone (O3) soundings, ship-borne O3 and nitrogen dioxide (NO2) observations in the western Mediterranean, tropospheric NO2 vertical column densities from the SCIAMACHY instrument, and aerosol optical depths (AOD) from the AERONET. The results show that on average, surface O3 levels are underestimated by 4 to 7% over the northern European EMEP stations while they are overestimated by 7–10% over the southern European EMEP stations and underestimated in the tropospheric column (by 10–20%). Particulate matter (PM) mass concentrations are underestimated by up to 60%, particularly in southern and eastern Europe, suggesting underestimated PM sources. Larger differences are calculated for individual aerosol components, particularly for organic and elemental carbon than for the total PM mass, indicating uncertainty in the combustion sources. Better agreement has been obtained for aerosol species over urban areas of the eastern Mediterranean, particularly for nss-SO42, attributed to the implementation of higher quality emission inventories for that area. Simulated AOD levels are lower than the AERONET observations by 10% on average, with average underestimations of 3% north of 40°N, attributed to the low anthropogenic emissions in the model and 22% south of 40°N, suggesting underestimated natural and resuspended dust emissions. Overall, the results reveal differences in the model performance between northern and southern Europe, suggesting significant differences in the representation of both anthropogenic and natural emissions in these regions. Budget analyses indicate that O3 and peroxyacetyl nitrate (PAN) are transported from the free troposphere (FT) to the planetary boundary layer over Europe, while other species follow the reverse path and are then advected away from the source region.

Measurements of Tropospheric NO2 in Romania Using a Zenith-Sky Mobile DOAS System and Comparisons with Satellite Observations

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) × 1015 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) × 1015 molec./cm2 (GOME-2) and (3.2 ± 3.2) × 1015 molec./cm2 (OMI), while average mobile measurements give (3.8 ± 0.8) × 1015 molec./cm2. Average ground measurements over “clean areas”, on 18 July 2011, give (2.5 ± 0.6) × 1015 molec./cm2 while the satellite observes a value of (1.8 ± 1.3) × 1015 molec./cm2.

MAX-DOAS measurements of NO<sub>2</sub>, HCHO and CHOCHO at a rural site in Southern China

Abstract. We performed MAX-DOAS measurements during the PRIDE-PRD2006 campaign in the Pearl River Delta region (PRD), China, for 4 weeks in July 2006 at a site located 60 km north of Guangzhou. The vertical distributions of NO2, HCHO, and CHOCHO were independently retrieved by an automated iteration method. The NO2 mixing ratios measured by MAX-DOAS showed reasonable agreement with the simultaneous, ground based in-situ data. The tropospheric NO2 vertical column densities (VCDs) observed by OMI on board EOS-Aura satellite were higher than with those by MAX-DOAS. The 3-D chemical transport model CMAQ overestimated the NO2 VCDs as well as the surface concentrations by about 65%. From this observation, a reduction of NOx emission strength in CMAQ seems to be necessary in order to well reproduce the NO2 observations. The average mixing ratios of HCHO and CHOCHO were 7 ppb and 0.4 ppb, respectively, higher than in other rural or semirural environments. The high ratio of 0.062 between CHOCHO and HCHO corresponds to the high VOCs reactivity and high HOx turnover rate consistent with other observations during the campaign.

Tropospheric NO<sub>2</sub> vertical column densities over Beijing: results of the first three years of ground-based MAX-DOAS measurements (2008–2011) and satellite validation

Abstract. 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.

Measuring tropospheric vertical distribution and vertical column density of NO2 by multi-axis differential optical absorption spectroscopy

The inversion method of the vertical profile and vertical column density (VCD) of tropospheric NO2 using multi-axis differential optical absorption spectroscopy (MAX-DOAS) is investigated in this paper. An inversion method of two-step procedure is operated. In this method firstly the aerosol vertical profile is retrieved. Then the vertical distribution of trace gases is retrieved based on the corresponding aerosol status. Nonlinear optimal estimation algorithm is extended to acquire NO2 profile to reduce the dependence of the inversion on priori information. It is more advantageous to automatically obtain trace gases profile. At first we investigate how to calculate some parameters (weighting function, the covariance matrices of measurement, and a priori information) of the algorithm and design nonlinear iteration strategy suited to the region where NO2 vertical distribution usually shows rapid variation. Then this inversion algorithm is verified by computer simulation in the cases of box profile and elevated profile of NO2. It is indicated that the distribution of NO2 below 2 km could be well rebuilt and the retrieval accuracy of surface-near NO2 volume mixing ratio is 0.6%. The study of how accurately this algorithm can rebuild the same true profile in three aerosol status of low aerosol, high aerosol and elevated aerosol indicates that similar retrieval results could be acquired. In addition, the effect of wrong aerosol status on the retrieving of NO2 profile and the error sources of this algorithm are analyzed. After that a continuous observation is reported in the city of Hefei. NO2 VCDs derived from MAX-DOAS are compared with those from satellite observations, and the correlation coefficient is 0.85. The surface-near NO2 concentrations measured by MAX-DOAS are compared with those from LP-DOAS, and the correlation coefficient is 0.76. In addition, the simplified MAX-DOAS inversion method of obtaining the trace gas profile usually uses invariable typical aerosol status as input. The comparison with the tropospheric NO2 VCD from simplified method indicates that the using of invariable typical aerosol status would cause large deviation of NO2 VCD, and its maximum relative deviation is about 112%. So exactly acquiring aerosol status, aerosol optical density especially, is necessary to exactly retrieve tropospheric NO2 vertical column density.

Trends in OMI NO<sub>2</sub> observations over the United States: effects of emission control technology and the economic recession

Abstract. Observations of tropospheric NO2 vertical column densities over the United States (US) for 2005–2011 are evaluated using the OMI Berkeley High Resolution (BEHR) retrieval algorithm. We assess changes in NO2 on day-of-week and interannual timescales to assess the impact of changes in emissions from mobile and non-mobile sources on the observed trends. We observe consistent decreases in cities across the US, with an average total reduction of 32 ± 7% across the 7 yr. Changes for large power plants have been more variable (−26 ± 12%) due to regionally-specific regulation policies. An increasing trend of 10–20% in background NO2 columns in the northwestern US is observed. We examine the impact of the economic recession on emissions and find that decreases in NO2 column densities over cities were moderate prior to the recession (−6 ± 5% yr−1), larger during the recession (−8 ± 5% yr−1), and then smaller after the recession (−3 ± 4% yr−1). Differences in the trends observed on weekdays and weekends indicate that prior to the economic recession, NO2 reductions were dominated by technological improvements to the light-duty vehicle fleet but that a decrease in diesel truck activity has contributed to emission reductions since the recession. We use the satellite observations to estimate a 34% decrease in NO2 from mobile sources in cities for 2005–2011 and use that value to infer changes in non-mobile sources. We find that reductions in NO2 from non-mobile sources in cities have been both more modest and more variable than NO2 reductions from mobile sources (−10 ± 13%).

Investigating the response of East Asian ozone to Chinese emission changes using a linear approach

To illuminate the issue of trans-boundary O3 pollution and regional O3 reduction policies in East Asia, we have investigated the East Asian ozone (O3) response to perturbations caused by Chinese anthropogenic emissions using the Community Multiscale Air Quality (CMAQ) model, a regional chemical transport model. The O3 responses have been examined for the range between −100 and +100% changes from the Chinese emissions level in 2004 in 10% intervals. We have found that springtime and summertime O3 responses both at the source and at the downwind areas can be regarded as linear over the range between −30 and +100% changes from the current emissions level. We therefore suggest that the perturbation between −30 and +100% is sufficiently small to avoid nonlinear chemical influence on O3 formation in a model experiment to investigate East Asian scale O3 source-receptor relationships. On the other hand, the O3 response is strongly nonlinear in April at Hong Kong, where the current NMVOCs/NOx ratio is low and the O3 production regime is easily moved to the NMVOCs sensitive region. The O3 responses to the NOx emission changes have been investigated using surface O3 concentrations at remote Japanese sites and tropospheric NO2 vertical column density (NO2 VCD) over central east China both with observations and with model simulations in springtime during 2003–2009. Analysis of satellite data shows that the observed range of NO2 VCD over central east China in 2003–2009 is the range between −25 and +34% from the 2004 level, which corresponds approximately to an emission variation between −21 and +29%. The O3 concentration in the downwind region during 2003–2009 responds linearly to a change of the NO2 VCD over central east China both in the model and in the observation. The corresponding O3 responses derived from surface observations at remote Japanese sites show linear features consistent with this expectation. The doubling of emissions, i.e., approximately 1.9-fold increase in the NO2 VCD from 2004, leads to O3 increments of 5ppbv and 8ppbv in the model and in the observation, respectively. The modeled O3 increase due to changes in NOx emission explains approximately 60% of the observed O3 trend at remote Japanese sites. Thus, approximately 40% of the observed O3 increase is unaccounted for by the NOx emissions growth.

Novel application of satellite and in-situ measurements to map surface-level NO<sub>2</sub> in the Great Lakes region

Abstract. Ozone Monitoring Instrument (OMI) tropospheric NO2 vertical column density data were used in conjunction with in-situ NO2 concentrations collected by permanently installed monitoring stations to infer 24 h surface-level NO2 concentrations at 0.1° (~11 km) resolution. The region examined included rural and suburban areas, and the highly industrialised area of Windsor, Ontario, which is situated directly across the US-Canada border from Detroit, MI. Photolytic NO2 monitors were collocated with standard NO2 monitors to provide qualitative data regarding NOz interference during the campaign. The accuracy of the OMI-inferred concentrations was tested using two-week integrative NO2 measurements collected with passive monitors at 18 locations, approximating a 15 km grid across the region, for 7 consecutive two-week periods. When compared with these passive results, satellite-inferred concentrations showed an 18% positive bias. The correlation of the passive monitor and OMI-inferred concentrations (R=0.69, n=115) was stronger than that for the passive monitor concentrations and OMI column densities (R=0.52), indicating that using a sparse network of monitoring sites to estimate concentrations improves the direct utility of the OMI observations. OMI-inferred concentrations were then calculated for four years to show an overall declining trend in surface NO2 concentrations in the region. Additionally, by separating OMI-inferred surface concentrations by wind direction, clear patterns in emissions and affected down-wind regions, in particular around the US-Canada border, were revealed.

A high spatial resolution retrieval of NO<sub> 2</sub> column densities from OMI: method and evaluation

Abstract. We present a new retrieval of tropospheric NO2 vertical column density from the Ozone Monitoring Instrument (OMI) based on high spatial and temporal resolution terrain and profile inputs. We compare our NO2 product, the Berkeley High-Resolution (BEHR) product, with operational retrievals and find that the operational retrievals are biased high (30 %) over remote areas and biased low (8 %) over urban regions. Additionally, we find non-negligible impacts on the retrieved NO2 column for terrain pressure (±20 %), albedo (±40 %), and NO2 vertical profile (−75 %–+10 %). We validate the operational and BEHR products using boundary layer aircraft observations from the Arctic Research of the Composition of the Troposphere from Aircraft and Satellites (ARCTAS-CA) field campaign which occurred in June 2008 in California. Results indicate that columns derived using our boundary layer extrapolation method show good agreement with satellite observations (R2 = 0.65–0.83; N = 68) and provide a more robust validation of satellite-observed NO2 column than those determined using full vertical spirals (R2 = 0.26; N = 5) as in previous work. Agreement between aircraft observations and the BEHR product (R2 = 0.83) is better than agreement with the operational products (R2 = 0.65–0.72). We also show that agreement between satellite and aircraft observations can be further improved (e.g. BEHR: R2 = 0.91) using cloud information from the Moderate Resolution Imaging Spectroradiometer (MODIS) instrument instead of the OMI cloud product. These results indicate that much of the variance in the operational products can be attributed to coarse resolution terrain pressure, albedo, and profile parameters implemented in the retrievals.

Detection of pollution transport events southeast of Mexico City using ground-based visible spectroscopy measurements of nitrogen dioxide

Abstract. This work presents ground based differential optical absorption spectroscopy (DOAS) measurements of nitrogen dioxide (NO2) during the MILAGRO field campaign in March 2006 at the Tenango del Aire research site located to the southeast of Mexico City. The DOAS NO2 column density measurements are used in conjunction with ceilometer, meteorological and surface nitric oxide (NO), nitrogen oxides (NOx) and total reactive nitrogen (NOy) measurements to analyze pollution transport events to the southeast of Mexico City during the MILARGO field campaign. The study divides the data set into three case study pollution transport events that occurred at the Tenango del Aire research site. The unique data set is then used to provide an in depth analysis of example days of each of the pollution transport events. An in depth analysis of 13 March 2006, a Case One day, shows the transport of several air pollution plumes during the morning through the Tenango del Aire research site when southerly winds are present and demonstrates how DOAS tropospheric NO2 vertical column densities (VCD), surface NO2 mixing ratios and ceilometer data are used to determine the vertical homogeneity of the pollution layer. The analysis of 18 March 2006, a Case Two day, shows that when northerly winds are present for the entire day, the air at the Tenango del Aire research site is relatively clean and no major pollution plumes are detected. Case 3 days are characterized by relatively clean air throughout the morning with large DOAS NO2 enhancements detected in the afternoon. The analysis of 28 March 2006 show the DOAS NO2 enhancements are likely due to lightning activity and demonstrate how suitable ground-based DOAS measruements are for monitoring anthropogenic and natural pollution sources that reside above the mixing layer.

Tropospheric NO<sub>2</sub> column densities deduced from zenith-sky DOAS measurements in Shanghai, China, and their application to satellite validation

Abstract. Zenith-sky scattered sunlight observations using differential optical absorption spectroscopy (DOAS) technique were carried out in Shanghai, China (31.3° N, 121.5° E) since December 2006. At this polluted urban site, the measurements provided NO2 total columns in the daytime. Here, we present a new method to extract time series of tropospheric vertical column densities (VCDs) of NO2 from these observations. The derived tropospheric NO2 VCDs are important quantities for the estimation of emissions and for the validation of satellite observations. Our method makes use of assumptions on the relative NO2 height profiles and the diurnal variation of stratospheric NO2 VCDs. The main error sources arise from the uncertainties in the estimated stratospheric slant column densities (SCDs) and the determination of tropospheric NO2 air mass factor (AMF). For a polluted site like Shanghai, the accuracy of our method is conservatively estimated to be <25% for solar zenith angle (SZA) lower than 70°. From simultaneously performed long-path DOAS measurements, the NO2 surface concentrations at the same site were observed and the corresponding tropospheric NO2 VCDs were estimated using the assumed seasonal NO2 profiles in the planetary boundary layer (PBL). By making a comparison between the tropospheric NO2 VCDs from zenith-sky and long-path DOAS measurements, it is found that the former provides more realistic information about total tropospheric pollution than the latter, so it's more suitable for satellite data validation. A comparison between the tropospheric NO2 VCDs from ground-based zenith-sky measurements and SCIAMACHY was also made. Satellite validation for a strongly polluted area is highly needed, but exhibits also a great challenge. Our comparison shows good agreement, considering in particular the different spatial resolutions between the two measurements. Remaining systematic deviations are most probably related to the uncertainties of satellite data caused by the assumptions on aerosol properties as well as the layer heights of aerosols and NO2.

FRESCO+: an improved O<sub>2</sub> A-band cloud retrieval algorithm for tropospheric trace gas retrievals

Abstract. The FRESCO (Fast Retrieval Scheme for Clouds from the Oxygen A-band) algorithm has been used to retrieve cloud information from measurements of the O2 A-band around 760 nm by GOME, SCIAMACHY and GOME-2. The cloud parameters retrieved by FRESCO are the effective cloud fraction and cloud pressure, which are used for cloud correction in the retrieval of trace gases like O3 and NO2. To improve the cloud pressure retrieval for partly cloudy scenes, single Rayleigh scattering has been included in an improved version of the algorithm, called FRESCO+. We compared FRESCO+ and FRESCO effective cloud fractions and cloud pressures using simulated spectra and one month of GOME measured spectra. As expected, FRESCO+ gives more reliable cloud pressures over partly cloudy pixels. Simulations and comparisons with ground-based radar/lidar measurements of clouds show that the FRESCO+ cloud pressure is about the optical midlevel of the cloud. Globally averaged, the FRESCO+ cloud pressure is about 50 hPa higher than the FRESCO cloud pressure, while the FRESCO+ effective cloud fraction is about 0.01 larger. The effect of FRESCO+ cloud parameters on O3 and NO2 vertical column density (VCD) retrievals is studied using SCIAMACHY data and ground-based DOAS measurements. We find that the FRESCO+ algorithm has a significant effect on tropospheric NO2 retrievals but a minor effect on total O3 retrievals. The retrieved SCIAMACHY tropospheric NO2 VCDs using FRESCO+ cloud parameters (v1.1) are lower than the tropospheric NO2VCDs which used FRESCO cloud parameters (v1.04), in particular over heavily polluted areas with low clouds. The difference between SCIAMACHY tropospheric NO2 VCDs v1.1 and ground-based MAXDOAS measurements performed in Cabauw, The Netherlands, during the DANDELIONS campaign is about −2.12×1014molec cm−2.

Systematic analysis of interannual and seasonal variations of model-simulated tropospheric NO<sub>2</sub> in Asia and comparison with GOME-satellite data

Abstract. Systematic analyses of interannual and seasonal variations of tropospheric NO2 vertical column densities (VCDs) based on GOME satellite data and the regional scale chemical transport model (CTM), Community Multi-scale Air Quality (CMAQ), are presented for the atmosphere over eastern Asia between 1996 and June 2003. A newly developed year-by-year emission inventory (REAS) was used in CMAQ. The horizontal distribution of annual averaged GOME NO2 VCDs generally agrees well with the CMAQ results. However, CMAQ/REAS results underestimate the GOME retrievals with factors of 2–4 over polluted industrial regions such as Central East China (CEC), a major part of Korea, Hong Kong, and central and western Japan. The most probable reasons for the underestimation typically over the CEC are accuracy of the basic energy statistic data, emission factors, and socio-economic data used for construction of emission inventory. For the Japan region, GOME and CMAQ NO2 data show reasonable agreement with respect to interannual variation and show no clear increasing trend. For CEC, GOME and CMAQ NO2 data indicate a very rapid increasing trend from 2000. Analyses of the seasonal cycle of NO2 VCDs show that GOME data have larger dips than CMAQ NO2 during February–April and September–November. Sensitivity experiments with fixed emission intensity reveal that the detection of emission trends from satellite in fall or winter has a larger error caused by the variability of meteorology. Examination during summer time and annual averaged NO2 VCDs are robust with respect to variability of meteorology and are therefore more suitable for analyses of emission trends. Analysis of recent trends of annual emissions in China shows that the increasing trends of 1996–1998 and 2000–2002 for GOME and CMAQ/REAS show good agreement, but the rate of increase by GOME is approximately 10–11% yr−1 after 2000; it is slightly steeper than CMAQ/REAS (8–9% yr−1). The greatest difference was apparent between the years 1998 and 2000: CMAQ/REAS only shows a few percentage points of increase, whereas GOME gives a greater than 8% yr−1 increase. The exact reason remains unclear, but the most likely explanation is that the emission trend based on the Chinese emission related statistics underestimates the rapid growth of emissions.

Comparison of 7 years of satellite‐borne and ground‐based tropospheric NO2 measurements around Milan, Italy

Tropospheric NO2 vertical column densities (VCDs) over the Lombardy region were retrieved from measurements of the Global Ozone Monitoring Experiment (GOME) spectrometer for the period 1996–2002 using a differential optical absorption method. This data set was compared with in situ measurements of NO2 at around 100 ground stations in the Lombardy region, northern Italy. The tropospheric NO2 VCDs are reasonably well correlated with the near‐surface measurements under cloud‐free conditions. However, the slope of the tropospheric VCDs versus ground measurements is higher in autumn‐winter than in spring‐summer. This effect is clearly reduced when the peroxyacetyl nitrate and nitric acid (HNO3) interferences of conventional NOx analyzers are taken into account. For a more quantitative comparison, the NO2 ground measurements were scaled to tropospheric VCDs using a seasonal NO2 vertical profile over northern Italy calculated by the Model of Ozone and Related Tracers 2 (MOZART‐2). The tropospheric VCDs retrieved from satellite and those determined from ground measurements agree well, with a correlation coefficient R = 0.78 and a slope close to 1 for slightly polluted stations. GOME cannot reproduce the high NO2 amounts over the most polluted stations, mainly because of the large spatial variability in the distribution of pollution within the GOME footprint. The yearly and weekly cycles of the tropospheric NO2 VCDs are similar for both data sets, with significantly lower values in the summer months and on Sundays, respectively. Considering the pollution level and high aerosol concentrations of this region, the agreement is very good. Furthermore, uncertainties in the ground‐based measurements, including the extrapolation to NO2 VCDs, might be as important as those of the NO2 satellite retrieval itself.

Weekly cycle of NO<sub>2</sub> by GOME measurements: a signature of anthropogenic sources

Abstract. Nitrogen oxides (NO+NO2=NOx and reservoir species) are important trace gases in the troposphere with impact on human health, atmospheric chemistry and climate. Besides natural sources (lightning, soil emissions) and biomass burning, fossil fuel combustion is estimated to be responsible for about 50% of the total production of NOx. Since human activity in industrialized countries largely follows a seven-day cycle, fossil fuel combustion is expected to be reduced during weekends. This "weekend effect" is well known from local, ground based measurements, but has never been analysed on a global scale before. The Global Ozone Monitoring Experiment (GOME) on board the ESA-satellite ERS-2 allows measurements of NO2 column densities. By estimating and subtracting the stratospheric column, and considering radiative transfer, vertical column densities (VCD) of tropospheric NO2 can be determined (e.g. Leue et al., 2001). We demonstrate the statistical analysis of weekly cycles of tropospheric NO2 VCDs for different regions of the world. In the cycles of the industrialized regions and cities in the US, Europe and Japan a clear Sunday minimum of tropospheric NO2 VCD can be seen. Sunday NO2 VCDs are about 25-50% lower than working day levels. Metropolitan areas with other religious and cultural backgrounds (Jerusalem, Mecca) show different weekly patterns corresponding to different days of rest. In China, no weekly pattern can be found. The presence of a weekly cycle in the measured tropospheric NO2 VCD may help to identify the different anthropogenic source categories. Furthermore, we estimated the lifetime of tropospheric NO2 by analysing the mean weekly cycle exemplarily over Germany, obtaining a value of about 6 h in summer and 18-24 h in winter.