NO2 Volume Mixing Ratios Research Articles

A CNN-SVR model for NO2 profile prediction based on MAX-DOAS observations: The influence of Chinese New Year overlapping the 2020 COVID-19 lockdown on vertical distributions of tropospheric NO2 in Nanjing, China

In this study, a hybrid model, the convolutional neural network-support vector regression model, was adopted to achieve prediction of the NO2 profile in Nanjing from January 2019 to March 2021. Given the sudden decline in NO2 in February 2020, the contribution of the Coronavirus Disease-19 (COVID-19) lockdown, Chinese New Year (CNY), and meteorological conditions to the reduction of NO2 was evaluated. NO2 vertical column densities (VCDs) from January to March 2020 decreased by 59.05% and 32.81%, relative to the same period in 2019 and 2021, respectively. During the period of 2020 COVID-19, the average NO2 VCDs were 50.50% and 29.96% lower than those during the pre-lockdown and post-lockdown periods, respectively. The NO2 volume mixing ratios (VMRs) during the 2020 COVID-19 lockdown significantly decreased below 400 m. The NO2 VMRs under the different wind fields were significantly lower during the lockdown period than during the pre-lockdown period. This phenomenon could be attributed to the 2020 COVID-19 lockdown. The NO2 VMRs before and after the CNY were significantly lower in 2020 than in 2019 and 2021 in the same period, which further proves that the decrease in NO2 in February 2020 was attributed to the COVID-19 lockdown. Pollution source analysis of an NO2 pollution episode during the lockdown period showed that the polluted air mass in the Beijing-Tianjin-Hebei was transported southwards under the action of the north wind, and the subsequent unfavorable meteorological conditions (local wind speed of < 2.0 m/sec) resulted in the accumulation of pollutants.

MAX-DOAS Measurements of Tropospheric NO2 and HCHO Vertical Profiles at the Longfengshan Regional Background Station in Northeastern China

The vertical profiles of nitrogen dioxide (NO2) and formaldehyde (HCHO) in the troposphere at the Longfengshan (LFS) regional atmospheric background station (127°36' E, 44°44' N, 330.5 m above sea level) from 24 October 2020 to 13 October 2021 were retrieved from solar scattering spectra by multi-axis differential optical absorption spectroscopy (MAX-DOAS). We analyzed the temporal variations of NO2 and HCHO as well as the sensitivity of ozone (O3) production to the concentration ratio of HCHO to NO2. The largest NO2 volume mixing ratios (VMRs) occur in the near-surface layer for each month, with high values concentrated in the morning and evening. HCHO has an elevated layer around the altitude of 1.4 km consistently. The means ± standard deviations of vertical column densities (VCDs) and near-surface VMRs were 4.69 ± 3.72 ×1015 molecule·cm-2 and 1.22 ± 1.09 ppb for NO2, and they were 1.19 ± 8.35 × 1016 molecule·cm-2 and 2.41 ± 3.26 ppb for HCHO. The VCDs and near-surface VMRs for NO2 were high in the cold months and low in the warm months, while HCHO presented the opposite. The larger near-surface NO2 VMRs appeared in the condition associated with lower temperature and higher humidity, but this relationship was not found between HCHO and temperature. We also found the O3 production at the Longfengshan station was mainly in the NOx-limited regime. This is the first study presenting the vertical distributions of NO2 and HCHO in the regional background atmosphere of northeastern China, which are significant to enhancing the understanding of background atmospheric chemistry and regional ozone pollution processes.

Evaluation of the coupled high-resolution atmospheric chemistry model system MECO(n) using in situ and MAX-DOAS NO&amp;lt;sub&amp;gt;2&amp;lt;/sub&amp;gt; measurements

Abstract. We present high spatial resolution (up to 2.2×2.2 km2) simulations focussed over south-west Germany using the online coupled regional atmospheric chemistry model system MECO(n) (MESSy-fied ECHAM and COSMO models nested n times). Numerical simulation of nitrogen dioxide (NO2) surface volume mixing ratios (VMRs) are compared to in situ measurements from a network with 193 locations including background, traffic-adjacent and industrial stations to investigate the model's performance in simulating the spatial and temporal variability of short-lived chemical species. We show that the use of a high-resolution and up-to-date emission inventory is crucial for reproducing the spatial variability and resulted in good agreement with the measured VMRs at the background and industrial locations with an overall bias of less than 10 %. We introduce a computationally efficient approach that simulates diurnal and daily variability in monthly-resolved anthropogenic emissions to resolve the temporal variability of NO2. MAX-DOAS (Multiple AXis Differential Optical Absorption Spectroscopy) measurements performed at Mainz (49.99∘ N, 8.23∘ E) were used to evaluate the simulated tropospheric vertical column densities (VCDs) of NO2. We propose a consistent and robust approach to evaluate the vertical distribution of NO2 in the boundary layer by comparing the individual differential slant column densities (dSCDs) at various elevation angles. This approach considers details of the spatial heterogeneity and sensitivity volume of the MAX-DOAS measurements while comparing the measured and simulated dSCDs. The effects of clouds on the agreement between MAX-DOAS measurements and simulations have also been investigated. For low elevation angles (≤8∘), small biases in the range of −14 % to +7 % and Pearson correlation coefficients in the range of 0.5 to 0.8 were achieved for different azimuth directions in the cloud-free cases, indicating good model performance in the layers close to the surface. Accounting for diurnal and daily variability in the monthly-resolved anthropogenic emissions was found to be crucial for the accurate representation of time series of measured NO2 VMR and dSCDs and is particularly critical when vertical mixing is suppressed, and the atmospheric lifetime of NO2 is relatively long.

Validation of TROPOMI tropospheric NO2 columns using dual-scan multi-axis differential optical absorption spectroscopy (MAX-DOAS) measurements in Uccle, Brussels

Abstract. Ground-based multi-axis differential optical absorption spectroscopy (MAX-DOAS) measurements of aerosols and tropospheric nitrogen dioxide (NO2) were carried out in Uccle (50.8∘ N, 4.35∘ E), Brussels, during 1 year from March 2018 until March 2019. The instrument was operated in both the UV and visible wavelength ranges in a dual-scan configuration consisting of two sub-modes: (1) an elevation scan in a fixed viewing azimuthal direction (the so-called main azimuthal direction) pointing to the northeast and (2) an azimuthal scan in a fixed low elevation angle (2∘). By applying a vertical profile inversion algorithm in the main azimuthal direction and a parameterization technique in the other azimuthal directions, near-surface NO2 volume mixing ratios (VMRs) and vertical column densities (VCDs) were retrieved in 10 different azimuthal directions. The dual-scan MAX-DOAS dataset allows for partly resolving the horizontal distribution of NO2 around the measurement site and studying its seasonal variations. Furthermore, we show that measuring the tropospheric NO2 VCDs in different azimuthal directions improves the spatial colocation with measurements from the Sentinel-5 Precursor (S5P), leading to a reduction of the spread in validation results. By using NO2 vertical profile information derived from the MAX-DOAS measurements, we also resolve a systematic underestimation in S5P NO2 data due to the use of inadequate a priori NO2 profile shape data in the satellite retrieval.

Dual ground-based MAX-DOAS observations in Vienna, Austria: Evaluation of horizontal and temporal NO2, HCHO, and CHOCHO distributions and comparison with independent data sets

Abstract We characterize two recently installed MAX-DOAS instruments in Vienna, Austria, and evaluate horizontal path-averaged near-surface nitrogen dioxide (NO2), formaldehyde (HCHO), and glyoxal (CHOCHO) volume mixing ratios (VMRs) over the urban area by applying a state-of-the-art retrieval approach. As Vienna is influenced by Pannonian continental climate, characterized by hot summers and cold winters, a temperature correction is introduced and applied to the NO2 differential slant column densities (DSCDs) retrieved in the visible spectral range to correct for the temperature dependence of the NO2 cross-section. The results show that not accounting for such a correction leads to an overestimation of absolute values by up to 15% in the winter season. Path-averaged NO2 VMRs from selected horizontal viewing directions are compared with surface NO2 VMRs from air quality monitoring stations located below and/or in close proximity to the particular MAX-DOAS line of sight. Good agreement between the two independent data sets is found, in particular during the summer season, with correlation coefficents ranging between 0.76 and 0.94. Seasonal and diurnal cycles of path-averaged NO2, HCHO, and CHOCHO VMRs are evaluated for a full year of measurements taken at the lowest elevation angles. While the highest daytime monthly averages of NO2 VMRs are found in winter, peaks of HCHO occur in summer. Highest amounts of CHOCHO conversely are observed over the course of the year, with the exception of summer. Seasonally-averaged diurnal cycles indicate that elevated NO2 and CHOCHO amounts are generally found in the morning hours and that there is a clear difference in trace gas amounts between weekdays and weekends when pointing at anthropogenic sources. The horizontal variabilty of tropospheric NO2, HCHO, and CHOCHO amounts is investigated by analyzing seasonally-averaged path-averaged VMRs, again obtained from measurements taken at the lowest elevation angles. The results show that highest amounts of NO2 and CHOCHO are found when the MAX-DOAS instruments are pointing towards the city center and/or towards busy roads and industrial areas, whereas highest amounts of HCHO are found over northern and western parts of Vienna, in particular in summer, which implies that anthropogenic sources are not the dominant drivers of HCHO production during that time of the year. Finally, the influence of wind direction and wind speed on tropospheric NO2, HCHO, and CHOCHO amounts is evaluted. The results show that tropospheric pollution levels over the city center of Vienna are highest at low wind speeds and wind directions from the Southeast.

Studies of the horizontal inhomogeneities in NO&amp;lt;sub&amp;gt;2&amp;lt;/sub&amp;gt; concentrations above a shipping lane using ground-based multi-axis differential optical absorption spectroscopy (MAX-DOAS) measurements and validation with airborne imaging DOAS measurements

Abstract. This study describes a novel application of an “onion-peeling” approach to multi-axis differential optical absorption spectroscopy (MAX-DOAS) measurements of shipping emissions aiming at investigating the strong horizontal inhomogeneities in NO2 over a shipping lane. To monitor ship emissions on the main shipping route towards the port of Hamburg, a two-channel (UV and visible) MAX-DOAS instrument was deployed on the island Neuwerk in the German Bight, 6–7 km south of the main shipping lane. Utilizing the fact that the effective light path length in the atmosphere depends systematically on wavelength, simultaneous measurements and DOAS retrievals in the UV and visible spectral ranges are used to probe air masses at different horizontal distances to the instrument to estimate two-dimensional pollutant distributions. Two case studies have been selected to demonstrate the ability to derive the approximate plume positions in the observed area. A situation with northerly wind shows high NO2 concentrations close to the measurement site and low values in the north of the shipping lane. The opposite situation with southerly wind, unfavorable for the on-site in situ instrumentation, demonstrates the ability to detect enhanced NO2 concentrations several kilometers away from the instrument. Using a Gaussian plume model, in-plume NO2 volume mixing ratios can be derived from the MAX-DOAS measurements. For validation, a comparison to airborne imaging DOAS measurements during the NOSE campaign in July 2013 is performed, showing good agreement between the approximate plume position derived from the onion-peeling MAX-DOAS and the airborne measurements as well as between the derived in-plume NO2 volume mixing ratios (VMRs).

OMI and Ground-Based In-Situ Tropospheric Nitrogen Dioxide Observations over Several Important European Cities during 2005-2014.

In this work we present the evolution of tropospheric nitrogen dioxide (NO2) content over several important European cities during 2005–2014 using space observations and ground-based in-situ measurements. The NO2 content was derived using the daily observations provided by the Ozone Monitoring Instrument (OMI), while the NO2 volume mixing ratio measurements were obtained from the European Environment Agency (EEA) air quality monitoring stations database. The European cities selected are: Athens (37.98° N, 23.72° E), Berlin (52.51° N, 13.41° E), Bucharest (44.43° N, 26.10° E), Madrid (40.38° N, 3.71° W), Lisbon (38.71° N, 9.13° W), Paris (48.85° N, 2.35° E), Rome (41.9° N, 12.50° E), and Rotterdam (51.91° N, 4.46° E). We show that OMI NO2 tropospheric column data can be used to assess the evolution of NO2 over important European cities. According to the statistical analysis, using the seasonal variation, we found good correlations (R > 0.50) between OMI and ground-based in-situ observations for all of the cities presented in this work. Highest correlation coefficients (R > 0.80) between ground-based monitoring stations and OMI observations were calculated for the cities of Berlin, Madrid, and Rome. Both types of observations, in-situ and remote sensing, show an NO2 negative trend for all of locations presented in this study.

The SPIRIT airborne instrument: a three-channel infrared absorption spectrometer with quantum cascade lasers for in situ atmospheric trace-gas measurements

An infrared absorption spectrometer called SPIRIT (SPectromètre Infra-Rouge In situ Toute altitude) has been developed for airborne measurements of trace gases in the troposphere. At least three different trace gases can be measured simultaneously every 1.6 s using the coupling of a single Robert multipass optical cell with three Quantum Cascade Lasers (QCLs), easily interchangeable to select species depending on the scientific objectives. Absorptions of the mid-infrared radiations by the species in the cell at reduced pressure (<40 hPa), with path lengths adjustable up to 167.78 m, are quantified using an HgCdTe photodetector cooled by Stirling cycle. The performances of the instrument are assessed: a linearity with a coefficient of determination R2 > 0.979 for the instrument response is found for CO, CH4, and NO2 volume mixing ratios under typical tropospheric conditions. In-flight comparisons with calibrated gas mixtures allow to show no instrumental drift correlated with atmospheric pressure and temperature changes (when vertical profiling) and to estimate the overall uncertainties in the measurements of CO, CH4, and NO2 to be 0.9, 22, and 0.5 ppbv, respectively. In-flight precision (1σ) for these species at 1.6 s sampling is 0.3, 5, and 0.3 ppbv, respectively.

Estimation of Surface NO2 Volume Mixing Ratio in Four Metropolitan Cities in Korea Using Multiple Regression Models with OMI and AIRS Data

Surface NO2 volume mixing ratio (VMR) at a specific time (13:45 Local time) (NO2 VMRST) and monthly mean surface NO2 VMR (NO2 VMRM) are estimated for the first time using three regression models with Ozone Monitoring Instrument (OMI) data in four metropolitan cities in South Korea: Seoul, Gyeonggi, Daejeon, and Gwangju. Relationships between the surface NO2 VMR obtained from in situ measurements (NO2 VMRIn-situ) and tropospheric NO2 vertical column density obtained from OMI from 2007 to 2013 were developed using regression models that also include boundary layer height (BLH) from Atmospheric Infrared Sounder (AIRS) and surface pressure, temperature, dew point, and wind speed and direction. The performance of the regression models is evaluated via comparison with the NO2 VMRIn-situ for two validation years (2006 and 2014). Of the three regression models, a multiple regression model shows the best performance in estimating NO2 VMRST and NO2 VMRM. In the validation period, the average correlation coefficient (R), slope, mean bias (MB), mean absolute error (MAE), root mean square error (RMSE), and percent difference between NO2 VMRIn-situ and NO2 VMRST estimated by the multiple regression model are 0.66, 0.41, −1.36 ppbv, 6.89 ppbv, 8.98 ppbv, and 31.50%, respectively, while the average corresponding values for the other two models are 0.75, 0.41, −1.40 ppbv, 3.59 ppbv, 4.72 ppbv, and 16.59%, respectively. All three models have similar performance for NO2 VMRM, with average R, slope, MB, MAE, RMSE, and percent difference between NO2 VMRIn-situ and NO2 VMRM of 0.74, 0.49, −1.90 ppbv, 3.93 ppbv, 5.05 ppbv, and 18.76%, respectively.

Improvement in Plume Dispersion Formulas for Stack Emissions Using Ground-based Imaging-DOAS Data

This study introduces a new method of combining Imaging Differential Optical Absorption Spectroscopy (Imaging-DOAS) data and plume dispersion formulas for power plant emissions to determine the threedimensional structure of a dispersing pollution plume and the spatial distributions of trace gas volume mixing ratios (VMRs) under conditions of negligible water droplet and aerosol effects on radiative transfer within the plume. This novel remote-sensing method, applied to a power plant stack plume, was used to calculate the twodimensional distributions of sulfur dioxide (SO2) and nitrogen dioxide (NO2) VMRs in stack emissions for the first time. High SO2 VMRs were observed only near the emission source, whereas high NO2 VMRs were observed at locations several hundreds of meters away from the initial emission. The results of this study demonstrate the capability of this new method as a tool for estimating plume dimensions and trace gas VMRs in power plant emissions.

First estimates of global free-tropospheric NO&amp;lt;sub&amp;gt;2&amp;lt;/sub&amp;gt; abundances derived using a cloud-slicing technique applied to satellite observations from the Aura Ozone Monitoring Instrument (OMI)

Abstract. We derive free-tropospheric NO2 volume mixing ratios (VMRs) by applying a cloud-slicing technique to data from the Ozone Monitoring Instrument (OMI) on the Aura satellite. In the cloud-slicing approach, the slope of the above-cloud NO2 column versus the cloud scene pressure is proportional to the NO2 VMR. In this work, we use a sample of nearby OMI pixel data from a single orbit for the linear fit. The OMI data include cloud scene pressures from the rotational-Raman algorithm and above-cloud NO2 vertical column density (VCD) (defined as the NO2 column from the cloud scene pressure to the top of the atmosphere) from a differential optical absorption spectroscopy (DOAS) algorithm. We compare OMI-derived NO2 VMRs with in situ aircraft profiles measured during the NASA Intercontinental Chemical Transport Experiment Phase B (INTEX-B) campaign in 2006. The agreement is generally within the estimated uncertainties when appropriate data screening is applied. We then derive a global seasonal climatology of free-tropospheric NO2 VMR in cloudy conditions. Enhanced NO2 in the free troposphere commonly appears near polluted urban locations where NO2 produced in the boundary layer may be transported vertically out of the boundary layer and then horizontally away from the source. Signatures of lightning NO2 are also shown throughout low and middle latitude regions in summer months. A profile analysis of our cloud-slicing data indicates signatures of lightning-generated NO2 in the upper troposphere. Comparison of the climatology with simulations from the global modeling initiative (GMI) for cloudy conditions (cloud optical depth &gt; 10) shows similarities in the spatial patterns of continental pollution outflow. However, there are also some differences in the seasonal variation of free-tropospheric NO2 VMRs near highly populated regions and in areas affected by lightning-generated NOx.

Local impact of solar variation on NO&amp;lt;sub&amp;gt;2&amp;lt;/sub&amp;gt; in the lower mesosphere and upper stratosphere from 2007 to 2012

Abstract. MIPAS/ENVISAT data of nighttime NO2 volume mixing ratios (VMR) from 2007 until 2012 between 40 km and 62 km altitude are compared with the geomagnetic Ap index and solar Lyman-α radiation. The local impact of variations in geomagnetic activity and solar radiation on the VMR of NO2 in the lower mesosphere and upper stratosphere in the Northern Hemisphere is investigated by means of superposed epoch analysis. Observations in the Northern Hemisphere show a clear 27-day period of the NO2 VMR. This is positively correlated with the geomagnetic Ap index at 60–70° N geomagnetic latitude but also partially correlated with the solar Lyman-α radiation. However, the dependency of NO2 VMR on geomagnetic activity can be distinguished from the impact of solar radiation. This indicates a direct response of NOx (NO + NO2) to geomagnetic activity, probably due to precipitating particles. The response is detected in the range between 46 km and 52 km altitude. The NO2 VMR epoch maxima due to geomagnetic activity is altitude-dependent and can reach up to 0.4 ppb, leading to mean production rates of 0.029 ppb (Ap d)−1. Observations in the Southern Hemisphere do not have the same significance due to a worse sampling of geomagnetic storm occurances. Variabilities due to solar variation occur at the same altitudes at 60–70° S geomagnetic latitude but cannot be analyzed as in the Northern Hemisphere. This is the first study showing the direct impact of electron precipitation on NOx at those altitudes in the spring/summer/autumn hemisphere.

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.

First-time remote sensing of NO2 vertical distributions in an urban street canyon using Topographic Target Light scattering Differential Optical Absorption Spectroscopy (ToTaL-DOAS)

Topographic Target Light scattering Differential Optical Absorption Spectroscopy (ToTaL-DOAS) measurements were performed in a street canyon in Gwangju, Korea (35°10′51.43″N, 126°52′53.74″E) during a period of 10 days in October 2010. NO2 slant volume mixing ratios (VMRs) at the lowest elevation angle (EL) of 1°, as obtained from ToTaL-DOAS measurements, were validated via comparisons with collocated in situ ground data, showing good agreement within a scatter range of 20% during the entire measurement period, and within a scatter range of 15% when cloudy days were excluded. For the first time, based on inversion calculations using ToTaL-DOAS data, we retrieved NO2 vertical distributions that consist of five layers (from 6 to 118m) for three measurement days. We obtained generally decreasing NO2 VMRs with altitude, whereas increased NO2 VMRs at two elevated layers (6–19m and 19–33m) were observed on 26 and 27 October. We obtained a coefficient of determination (R2) of 0.87 (0.61) between slant VMRs at 1° EL (retrieved NO2 VMRs in the layer from 6m to 19m) and in situ data, with the scatter of the correlation being within the 15% (10%) range. The relation between retrieved NO2 VMRs at 6–19m and slant VMRs at 1° EL yielded an R2 value of 0.97, with the scatter of the correlation being within the 5% range. The results demonstrate that the ToTaL-DOAS technique is a useful tool in identifying the temporal and vertical characteristics of NO2 VMRs in an urban street canyon with a complex geometry.

Ability of the MAX-DOAS method to derive profile information for NO&amp;lt;sub&amp;gt;2&amp;lt;/sub&amp;gt;: can the boundary layer and free troposphere be separated?

Abstract. Multiple Axis Differential Optical Absorption Spectroscopy (MAX-DOAS) instruments can measure from the ground the absorption by nitrogen dioxide (NO2) of scattered sunlight seen in multiple viewing directions. This paper studies the potential of this technique to derive the vertical distribution of NO2 in the troposphere. Such profile information is essential for detailed comparisons of MAX-DOAS retrievals with other measurement techniques for NO2, e.g. with a lidar or from space. The retrieval algorithm used is based on a pre-calculated look-up table and assumes homogeneous mixing of aerosols and NO2 in layers extending from the surface to a variable height. Two retrieval models are compared: one including and one excluding an elevated NO2 layer at a fixed altitude in the free troposphere. An ensemble technique is applied to derive retrieval uncertainties. Sensitivity studies demonstrate that NO2 in the free troposphere can only be retrieved accurately if: (i) the retrieved boundary layer profiles for aerosols and NO2 correspond to the real ones, (ii) if the right a-priori choice is made for the (average) height of free tropospheric NO2, and (iii) if all other error sources are very low. It is shown that retrieval models that are capable of accurate NO2 retrievals in the free troposphere, i.e. models not constrained too much by a-priori assumptions, have as a major disadvantage that they will frequently find free tropospheric NO2, also when it is not present in reality. This is a consequence of the fact that NO2 in the free troposphere is poorly constrained by the MAX-DOAS observations, especially for high aerosol optical thickness values in the boundary layer. Retrieval of free tropospheric NO2 is therefore sensitive to a large number of error sources. For this reason it is advised to firmly constrain free tropospheric NO2 in MAX-DOAS retrieval models used for applications such as satellite validation. This effectively makes free tropospheric NO2 a source of error for MAX-DOAS retrieval of NO2 profiles in the boundary layer. A comparison was performed with independent data, based on MAX-DOAS observations done at the CINDI campaign, held in the Netherlands in 2009. Comparison with lidar partial tropospheric NO2 columns showed a correlation of 0.78, and an average difference of 0.1× 1015 molec cm−2. The diurnal evolution of the NO2 volume mixing ratio measured by in-situ monitors at the surface and averaged over five days with cloud-free mornings, compares well to the MAX-DOAS retrieval: a correlation was found of 0.94, and an average difference of 0.04 ppb.

Combined measurements of a UV mini MAX-DOAS system and a TX for retrieval of ambient trace gas mixing ratio: Comparisons with combined RTM and MAX-DOAS methods

Abstract A measurement method combining multi-axis differential optical absorption spectroscopy (MAX-DOAS) and a transmissometer (TX) is introduced as a means of retrieving surface trace gas mixing ratios in ambient air. The combined measurement method was utilized to derive surface NO2 mixing ratios from 27 March to 11 May 2007 in Seoul, Korea. To convert the differential slant column density (DSCD) to the volume mixing ratio (VMR), the light path length (LPL) along the MAX-DOAS line of sight was derived using the light extinction coefficient and Angstrom exponent data obtained by a TX and sunphotometer, respectively. Temporal variations of the NO2 VMRs at the 0–1 km layer obtained from radiative transfer model (RTM) simulations coupled with MAX-DOAS data show similar patterns, but with reduced magnitudes, to the ground level data and those of the combined MAX-DOAS and TX measurements at 0.08 km. The NO2 VMRs retrieved by the combined measurement were in agreement with those obtained from the RTM simulations coupled with MAX-DOAS data and the in-situ measurements within 40 and 50%, respectively. The coefficient of determination (R2) of 0.75 was obtained between the combined measurement data sets and those of the RTM simulations coupled with MAX-DOAS data whereas that between the combined measurement data sets and those of the in-situ measurements was 0.53. The coefficient of determination (R2) between the data sets derived from the RTM simulations coupled with MAX-DOAS data and those of the in-situ measurements was 0.67 with the scatter of the correlation within the 50% range.

Eight-component retrievals from ground-based MAX-DOAS observations

Abstract. We attempt for the first time to retrieve lower-tropospheric vertical profile information for 8 quantities from ground-based Multi-Axis Differential Optical Absorption Spectroscopy (MAX-DOAS) observations. The components retrieved are the aerosol extinction coefficients at two wavelengths, 357 and 476 nm, and NO2, HCHO, CHOCHO, H2O, SO2, and O3 volume mixing ratios. A Japanese MAX-DOAS profile retrieval algorithm, version 1 (JM1), is applied to observations performed at Cabauw, the Netherlands (51.97° N, 4.93° E), in June–July 2009 during the Cabauw Intercomparison campaign of Nitrogen Dioxide measuring Instruments (CINDI). Of the retrieved profiles, we focus here on the lowest-layer data (mean values at altitudes 0–1 km), where the sensitivity is usually highest owing to the longest light path. In support of the capability of the multi-component retrievals, we find reasonable overall agreement with independent data sets, including a regional chemical transport model (CHIMERE) and in situ observations performed near the surface (2–3 m) and at the 200-m height level of the tall tower in Cabauw. Plumes of enhanced HCHO and SO2 were likely affected by biogenic and ship emissions, respectively, and an improvement in their emission strengths is suggested for better agreement between CHIMERE simulations and MAX-DOAS observations. Analysis of air mass factors indicates that the horizontal spatial representativeness of MAX-DOAS observations is about 3–15 km (depending mainly on aerosol extinction), comparable to or better than the spatial resolution of current UV-visible satellite observations and model calculations. These demonstrate that MAX-DOAS provides multi-component data useful for the evaluation of satellite observations and model calculations and can play an important role in bridging different data sets having different spatial resolutions.

Derivation of the Ambient Nitrogen Dioxide Mixing Ratio over a Traffic Road Site Based on Simultaneous Measurements Using a Ground-based UV Scanning Spectrograph

Simultaneous measurements using a scanning spectrograph system and transmissometer were performed for the first time over an urban site in Gwangju, Korea, to derive the ambient NO2 volume mixing ratio. The differential slant column densities retrieved from the scanning spectrograph system were converted to volume mixing ratios using the light traveling distance along the scanning line of sight derived from the transmissometer light extinction coefficients. To assess the performance of this system, we compared the derived NO2 volume mixing ratios with those measured by an in situ chemiluminescence monitor under various atmospheric conditions. For a cloudless atmosphere, the linear correlation coefficient (R) between the two data sets (i.e., data derived from the scanning spectrograph and from the in situ monitor) was 0.81; the value for a cloudy atmosphere was 0.69. The two sets of NO2 volume mixing ratios were also compared for various wind speeds. We also consider the measurement errors, as estimated from an error propagation analysis.

Validation of NO&amp;lt;sub&amp;gt;2&amp;lt;/sub&amp;gt; and NO from the Atmospheric Chemistry Experiment (ACE)

Abstract. Vertical profiles of NO2 and NO have been obtained from solar occultation measurements by the Atmospheric Chemistry Experiment (ACE), using an infrared Fourier Transform Spectrometer (ACE-FTS) and (for NO2) an ultraviolet-visible-near-infrared spectrometer, MAESTRO (Measurement of Aerosol Extinction in the Stratosphere and Troposphere Retrieved by Occultation). In this paper, the quality of the ACE-FTS version 2.2 NO2 and NO and the MAESTRO version 1.2 NO2 data are assessed using other solar occultation measurements (HALOE, SAGE II, SAGE III, POAM III, SCIAMACHY), stellar occultation measurements (GOMOS), limb measurements (MIPAS, OSIRIS), nadir measurements (SCIAMACHY), balloon-borne measurements (SPIRALE, SAOZ) and ground-based measurements (UV-VIS, FTIR). Time differences between the comparison measurements were reduced using either a tight coincidence criterion, or where possible, chemical box models. ACE-FTS NO2 and NO and the MAESTRO NO2 are generally consistent with the correlative data. The ACE-FTS and MAESTRO NO2 volume mixing ratio (VMR) profiles agree with the profiles from other satellite data sets to within about 20% between 25 and 40 km, with the exception of MIPAS ESA (for ACE-FTS) and SAGE II (for ACE-FTS (sunrise) and MAESTRO) and suggest a negative bias between 23 and 40 km of about 10%. MAESTRO reports larger VMR values than the ACE-FTS. In comparisons with HALOE, ACE-FTS NO VMRs typically (on average) agree to ±8% from 22 to 64 km and to +10% from 93 to 105 km, with maxima of 21% and 36%, respectively. Partial column comparisons for NO2 show that there is quite good agreement between the ACE instruments and the FTIRs, with a mean difference of +7.3% for ACE-FTS and +12.8% for MAESTRO.

Vertical profiles of lightning-produced NO&amp;lt;sub&amp;gt;2&amp;lt;/sub&amp;gt; enhancements in the upper troposphere observed by OSIRIS

Abstract. The purpose of this study is to perform a global search of the upper troposphere (z≥10 km) for enhancements of nitrogen dioxide and determine their sources. This is the first application of satellite-based limb scattering to study upper tropospheric NO2. We have searched two years (May 2003–May 2005) of OSIRIS (Optical Spectrograph and Infrared Imager System) operational NO2 concentrations (version 2.3/2.4) to find large enhancements in the observations by comparing with photochemical box model calculations and by identifying local maxima in NO2 volume mixing ratio. We find that lightning is the main production mechanism responsible for the large enhancements in OSIRIS NO2 observations as expected. Similar patterns in the abundances and spatial distribution of the NO2 enhancements are obtained by perturbing the lightning within the GEOS-Chem 3-dimensional chemical transport model. In most cases, the presence of lightning is confirmed with coincident imagery from LIS (Lightning Imaging Sensor) and the spatial extent of the NO2 enhancement is mapped using nadir observations of tropospheric NO2 at high spatial resolution from SCIAMACHY (Scanning Imaging Absorption Spectrometer for Atmospheric Chartography) and OMI (Ozone Monitoring Instrument). The combination of the lightning and chemical sensors allows us to investigate globally the role of lightning to the abundance of NO2 in the upper troposphere (UT). Lightning contributes 60% of the tropical upper tropospheric NO2 in GEOS-Chem simulations. The spatial and temporal distribution of NO2 enhancements from lightning (May 2003–May 2005) is investigated. The enhancements generally occur at 12 to 13 km more frequently than at 10 to 11 km. This is consistent with the notion that most of the NO2 is forming and persisting near the cloud top altitude in the tropical upper troposphere. The latitudinal distribution is mostly as expected. In general, the thunderstorms exhibiting weaker vertical development (e.g. 11≤z≤13 km) extend latitudinally as far poleward as 45° but the thunderstorms with stronger vertical development (z≥14 km) tend to be located within 33° of the equator. There is also the expected hemispheric asymmetry in the frequency of the NO2 enhancements, as most were observed in the northern hemisphere for the period analyzed.