Multi-axis Differential Optical Absorption Spectroscopy Research Articles

Vertical distributions of tropospheric SO2 based on MAX-DOAS observations: Investigating the impacts of regional transport at different heights in the boundary layer

Information on the vertical distribution of air pollutants is essential for understanding their spatiotemporal evolution underlying urban atmospheric environment. This paper presents the SO2 profiles based on ground-based Multi-Axis Differential Optical Absorption Spectroscopy (MAX-DOAS) measurements from March 2018 to February 2019 in Hefei, East China. SO2 decrease rapidly with increasing heights in the warm season, while lifted layers were observed in the cold season, indicating accumulation or long-range transport of SO2 in different seasons might occur at different heights. The diurnal variations of SO2 were roughly consistent for all four seasons, exhibiting the minimum at noon and higher values in the morning and late afternoon. Lifted layers of SO2 were observed in the morning for fall and winter, implying the accumulation or transport of SO2 in the morning mainly occurred at the top of the boundary layer. The bivariate polar plots showed that weighted SO2 concentrations in the lower altitude were weakly dependent on wind, but in the middle and upper altitudes, higher weighted SO2 concentrations were observed under conditions of middle-high wind speed. Concentration weighted trajectory (CWT) analysis suggested that potential sources of SO2 in spring and summer were local and transported mainly occurred in the lower altitude from southern and eastern areas; while in fall and winter, SO2 concentrations were deeply affected by long-range transport from northwestern and northern polluted regions in the middle and upper altitudes. Our findings provide new insight into the impacts of regional transport at different heights in the boundary layer on SO2 pollution.

Estimation of reactive inorganic iodine fluxes in the Indian and Southern Ocean marine boundary layer

Abstract. Iodine chemistry has noteworthy impacts on the oxidising capacity of the marine boundary layer (MBL) through the depletion of ozone (O3) and changes to HOx (OH∕HO2) and NOx (NO∕NO2) ratios. Hitherto, studies have shown that the reaction of atmospheric O3 with surface seawater iodide (I−) contributes to the flux of iodine species into the MBL mainly as hypoiodous acid (HOI) and molecular iodine (I2). Here, we present the first concomitant observations of iodine oxide (IO), O3 in the gas phase, and sea surface iodide concentrations. The results from three field campaigns in the Indian Ocean and the Southern Ocean during 2015–2017 are used to compute reactive iodine fluxes in the MBL. Observations of atmospheric IO by multi-axis differential optical absorption spectroscopy (MAX-DOAS) show active iodine chemistry in this environment, with IO values up to 1 pptv (parts per trillion by volume) below latitudes of 40∘ S. In order to compute the sea-to-air iodine flux supporting this chemistry, we compare previously established global sea surface iodide parameterisations with new region-specific parameterisations based on the new iodide observations. This study shows that regional changes in salinity and sea surface temperature play a role in surface seawater iodide estimation. Sea–air fluxes of HOI and I2, calculated from the atmospheric ozone and seawater iodide concentrations (observed and predicted), failed to adequately explain the detected IO in this region. This discrepancy highlights the need to measure direct fluxes of inorganic and organic iodine species in the marine environment. Amongst other potential drivers of reactive iodine chemistry investigated, chlorophyll a showed a significant correlation with atmospheric IO (R=0.7 above the 99 % significance level) to the north of the polar front. This correlation might be indicative of a biogenic control on iodine sources in this region.

A feasibility study to use machine learning as an inversion algorithm for aerosol profile and property retrieval from multi-axis differential absorption spectroscopy measurements

Abstract. In this study, we explore a new approach based on machine learning (ML) for deriving aerosol extinction coefficient profiles, single-scattering albedo and asymmetry parameter at 360 nm from a single multi-axis differential optical absorption spectroscopy (MAX-DOAS) sky scan. Our method relies on a multi-output sequence-to-sequence model combining convolutional neural networks (CNNs) for feature extraction and long short-term memory networks (LSTMs) for profile prediction. The model was trained and evaluated using data simulated by Vector Linearized Discrete Ordinate Radiative Transfer (VLIDORT) v2.7, which contains 1 459 200 unique mappings. From the simulations, 75 % were randomly selected for training and the remaining 25 % for validation. The overall error of estimated aerosol properties (1) for total aerosol optical depth (AOD) is -1.4±10.1 %, (2) for the single-scattering albedo is 0.1±3.6 %, and (3) for the asymmetry factor is -0.1±2.1 %. The resulting model is capable of retrieving aerosol extinction coefficient profiles with degrading accuracy as a function of height. The uncertainty due to the randomness in ML training is also discussed.

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.

Inter-comparison of MAX-DOAS measurements of tropospheric HONO slant column densities and vertical profiles during the CINDI-2 campaign

Abstract. We present the inter-comparison of delta slant column densities (SCDs) and vertical profiles of nitrous acid (HONO) derived from measurements of different multi-axis differential optical absorption spectroscopy (MAX-DOAS) instruments and using different inversion algorithms during the Second Cabauw Inter-comparison campaign for Nitrogen Dioxide measuring Instruments (CINDI-2) in September 2016 at Cabauw, the Netherlands (51.97∘ N, 4.93∘ E). The HONO vertical profiles, vertical column densities (VCDs), and near-surface volume mixing ratios are compared between different MAX-DOAS instruments and profile inversion algorithms for the first time. Systematic and random discrepancies of the HONO results are derived from the comparisons of all data sets against their median values. Systematic discrepancies of HONO delta SCDs are observed in the range of ±0.3×1015 molec. cm−2, which is half of the typical random discrepancy of 0.6×1015 molec. cm−2. For a typical high HONO delta SCD of 2×1015 molec. cm−2, the relative systematic and random discrepancies are about 15 % and 30 %, respectively. The inter-comparison of HONO profiles shows that both systematic and random discrepancies of HONO VCDs and near-surface volume mixing ratios (VMRs) are mostly in the range of ∼±0.5×1014 molec. cm−2 and ∼±0.1 ppb (typically ∼20 %). Further we find that the discrepancies of the retrieved HONO profiles are dominated by discrepancies of the HONO delta SCDs. The profile retrievals only contribute to the discrepancies of the HONO profiles by ∼5 %. However, some data sets with substantially larger discrepancies than the typical values indicate that inappropriate implementations of profile inversion algorithms and configurations of radiative transfer models in the profile retrievals can also be an important uncertainty source. In addition, estimations of measurement uncertainties of HONO dSCDs, which can significantly impact profile retrievals using the optimal estimation method, need to consider not only DOAS fit errors, but also atmospheric variability, especially for an instrument with a DOAS fit error lower than ∼3×1014 molec. cm−2. The MAX-DOAS results during the CINDI-2 campaign indicate that the peak HONO levels (e.g. near-surface VMRs of ∼0.4 ppb) often appeared in the early morning and below 0.2 km. The near-surface VMRs retrieved from the MAX-DOAS observations are compared with those measured using a co-located long-path DOAS instrument. The systematic differences are smaller than 0.15 and 0.07 ppb during early morning and around noon, respectively. Since true HONO values at high altitudes are not known in the absence of real measurements, in order to evaluate the abilities of profile inversion algorithms to respond to different HONO profile shapes, we performed sensitivity studies using synthetic HONO delta SCDs simulated by a radiative transfer model with assumed HONO profiles. The tests indicate that the profile inversion algorithms based on the optimal estimation method with proper configurations can reproduce the different HONO profile shapes well. Therefore we conclude that the features of HONO accumulated near the surface derived from MAX-DOAS measurements are expected to represent the ambient HONO profiles well.

Validation of Water Vapor Vertical Distributions Retrieved from MAX-DOAS over Beijing, China

Water vapor vertical profiles are important in numerical weather prediction, moisture transport, and vertical flux calculation. This study presents the Multi-Axis Differential Optical Absorption Spectroscopy (MAX-DOAS) retrieval algorithm for water vapor vertical profiles and the retrieved results are validated with corresponding independent datasets under clear sky. The retrieved Vertical Column Densities (VCDs) and surface concentrations are validated with the Aerosol Robotic Network (AERONET) and National Climatic Data Centre (NCDC) datasets, achieving good correlation coefficients (R) of 0.922 and 0.876, respectively. The retrieved vertical profiles agree well with weekly balloon-borne radiosonde measurements. Furthermore, the retrieved water vapor concentrations at different altitudes (100–2000 m) are validated with the corresponding European Centre for Medium-range Weather Forecasts (ECMWF) ERA-interim datasets, achieving a correlation coefficient (R) varying from 0.695 to 0.857. The total error budgets for the surface concentrations and VCDs are 31% and 38%, respectively. Finally, the retrieval performance of the MAX-DOAS algorithm under different aerosol loads is evaluated. High aerosol loads obstruct the retrieval of surface concentrations and VCDs, with surface concentrations more liable to severe interference from such aerosol loads. To summarize, the feasibility of detecting water vapor profiles using MAX-DOAS under clear sky is confirmed in this work.

Measuring the Vertical Profiles of Aerosol Extinction in the Lower Troposphere by MAX-DOAS at a Rural Site in the North China Plain

Ground-based multi-axis differential optical absorption spectroscopy (MAX-DOAS) measurements were performed during the summer (13 June–20 August) of 2014 at a rural site in North China Plain. The vertical profiles of aerosol extinction (AE) in the lower troposphere were retrieved to analyze the temporal variations of AE profiles, near-surface AE, and aerosol optical depth (AOD). The average AOD and near-surface AE over the period of study were 0.51 ± 0.26 and 0.33 ± 0.18 km−1 during the effective observation period, respectively. High AE events and elevated AE layers were identified based on the time series of hourly AE profiles, near-surface AEs and AODs. It is found that in addition to the planetary boundary layer height (PBLH) and relative humidity (RH), the variations in the wind field have large impacts on the near-surface AE, AOD, and AE profile. Among 16 wind sectors, higher AOD or AE occur mostly in the directions of the cities upstream. The diurnal variations of the AE profiles, AODs and near-surface AEs are significant and influenced mainly by the source emissions, PBLH, and RH. The AE profile shape from MAX-DOAS measurement is generally in agreement with that from light detection and ranging (lidar) observations, although the AE absolute levels are different. Overall, ground-based MAX-DOAS can serve as a supplement to measure the AE vertical profiles in the lower troposphere.

Retrieving tropospheric NO<sub>2</sub> vertical column densities around the city of Beijing and estimating NO<sub><i>x</i></sub> emissions based on car MAX-DOAS measurements

Abstract. We carried out 19 city-circle-around car multi-axis differential optical absorption spectroscopy (MAX-DOAS) experiments on the 6th Ring Road of Beijing in January, September, and October 2014. The tropospheric vertical column densities (VCDs) of NO2 were retrieved from measured spectra by the MAX-DOAS technique and used to estimate the emissions of NOx (≡NO+NO2) from urban Beijing during the experimental periods. The offline LAPS-WRF-CMAQ model system was used to simulate the wind fields by assimilation of observational data and calculate the NO2-to-NOx concentration ratios, both of which are also needed for the estimation of NOx emissions. The NOx emissions in urban Beijing for the different months derived from the car MAX-DOAS measurements in this study were compared to the multi-resolution emission inventory in China for 2012 (MEIC 2012). Our car MAX-DOAS measurements showed higher NO2 VCD in January than in the other two months. The wind field had obvious impacts on the spatial distribution of NO2 VCD, with the mean NO2 VCD along the 6th Ring Road typically being higher under the southerly wind than under the northerly wind. In addition to the seasonal difference, the journey-to-journey variations of estimated NOx emission rates (ENOx) were large even within the same month, mainly due to uncertainties in the calculations of wind speed, the ratio of NO2 and NOx concentration, and the decay rate of NOx from the emission sources to the measured positions under different meteorological conditions. The ranges of ENOx during the heating and non-heating periods were 22.6×1025 to 31.3×1025 and 9.6×1025 to 12.0×1025 molec. s−1, respectively. The average ENOx values in the heating and non-heating periods were 26.9±6.1×1025 molec. s−1 and 11.0±1.2×1025 molec. s−1, respectively. The uncertainty range of ENOx was 20 %–52 %. The monthly emission rates from MEIC 2012 are found to be lower than the estimated ENOx, particularly in January. Our results provide important information and datasets for the validation of satellite products and also show how car MAX-DOAS measurements can be used effectively for dynamic monitoring and updating of the NOx emissions from megacities such as Beijing.

MAX-DOAS measurements of tropospheric NO<sub>2</sub> and HCHO in Munich and the comparison to OMI and TROPOMI satellite observations

Abstract. We present two-dimensional scanning Multi-AXis Differential Optical Absorption Spectroscopy (MAX-DOAS) observations of nitrogen dioxide (NO2) and formaldehyde (HCHO) in Munich. Vertical columns and vertical distribution profiles of aerosol extinction coefficient, NO2 and HCHO are retrieved from the 2D MAX-DOAS observations. The measured surface aerosol extinction coefficients and NO2 mixing ratios derived from the retrieved profiles are compared to in situ monitoring data, and the surface NO2 mixing ratios show a good agreement with in situ monitoring data with a Pearson correlation coefficient (R) of 0.91. The aerosol optical depths (AODs) show good agreement as well (R = 0.80) when compared to sun photometer measurements. Tropospheric vertical column densities (VCDs) of NO2 and HCHO derived from the MAX-DOAS measurements are also used to validate Ozone Monitoring Instrument (OMI) and TROPOspheric Monitoring Instrument (TROPOMI) satellite observations. Monthly averaged data show a good correlation; however, satellite observations are on average 30 % lower than the MAX-DOAS measurements. Furthermore, the MAX-DOAS observations are used to investigate the spatiotemporal characteristic of NO2 and HCHO in Munich. Analysis of the relations between aerosol, NO2 and HCHO shows higher aerosol-to-HCHO ratios in winter, which reflects a longer atmospheric lifetime of secondary aerosol and HCHO during winter. The analysis also suggests that secondary aerosol formation is the major source of these aerosols in Munich.

Primary Evaluation of the GCOM-C Aerosol Products at 380 nm Using Ground-Based Sky Radiometer Observations

The Global Change Observation Mission-Climate (GCOM-C) is currently the only satellite sensor providing aerosol optical thickness (AOT) in the ultraviolet (UV) region during the morning overpass time. The observations in the UV region are important to detect the presence of absorbing aerosols in the atmosphere. The recently available GCOM-C dataset of AOT at 380 nm for January to September 2019 were evaluated using ground-based SKYNET sky radiometer measurements at Chiba, Japan (35.62° N, 140.10° E) and Phimai, central Thailand (15.18° N, 102.56° E), representing urban and rural sites, respectively. AOT retrieved from sky radiometer observations in Chiba and Phimai was compared with coincident AERONET and multi-axis differential optical absorption spectroscopy (MAX-DOAS) AOT values, respectively. Under clear sky conditions, the datasets showed good agreement. The sky radiometer and GCOM-C AOT values showed a positive correlation (R) of ~0.73 for both sites, and agreement between the datasets was mostly within ±0.2 (the number of coincident points at both sites was less than 50 for the coincidence criterion of ≤30 km). At Chiba, greater differences in the AOT values were primarily related to cloud screening in the datasets. The mean bias error (MBE) (GCOM-C – sky radiometer) for the Chiba site was −0.02 for a coincidence criterion of ≤10 km. For a similar coincidence criterion, the MBE values were higher for observations at the Phimai site. This difference was potentially related to the strong influence of biomass burning during the dry season (Jan–Apr). The diurnal variations in AOT, inferred from the combination of GCOM-C and ozone monitoring instrument (OMI) observations, showed good agreement with the sky radiometer data, despite the differences in the absolute AOT values. Over Phimai, the AOT diurnal variations from the satellite and sky radiometer observations were different, likely due to the large differences in the AOT values during the dry season.

Surface ozone exceedances in Melbourne, Australia are shown to be under NOx control, as demonstrated using formaldehyde:NO2 and glyoxal:formaldehyde ratios

Two and a half years of multi-axis differential optical absorption spectroscopy (MAX-DOAS) measurements of nitrogen dioxide (NO2), formaldehyde (HCHO) and glyoxal (CHOCHO) are presented alongside in-situ ozone (O3) measurements in Melbourne, Australia. Seasonal and diurnal cycles, vertical profiles and relationships with key meteorological variables are provided. NO2 and CHOCHO were found at highest concentration for low wind speeds implying that their sources were predominantly localised and anthropogenic. HCHO showed an exponential relationship with temperature and a strong wind direction dependence from the northern and eastern sectors, and therefore most likely originated from oxidation of biogenic volatile organic compounds (VOCs) from surrounding forested and rural areas. The glyoxal:formaldehyde ratio (Rgf), reported for the first time in Australia, was consistently high compared to values elsewhere in the world with a mean of 0.105 ± 0.0503 and tended to increase with increasing anthropogenic influence. The HCHO:NO2 ratio (Rfn) was used to characterise tropospheric ozone formation conditions. A strong relationship was found between high temperature, low Rgf, high Rfn and high ozone surface concentrations. Therefore, we propose that both Rgf and Rfn may be useful indicators of tropospheric ozone production regimes and concentrations. The Rfn showed that the vast majority of high ozone production episodes occurred under NOx-limited conditions, suggesting that surface ozone pollution events in Melbourne could be curtailed using NOx emission controls.

Recommendations for spectral fitting of SO<sub>2</sub> from miniature multi-axis differential optical absorption spectroscopy (MAX-DOAS) measurements

Abstract. Fitting sulfur dioxide (SO2) differential slant column densities (dSCDs) from multi-axis differential optical absorption spectroscopy (MAX-DOAS) measurements of scattered sunlight is challenging because actinic light intensity is low in the wavelength regions where the SO2 absorption features are strongest. SO2 dSCDs were fit with different wavelength windows (λlow to λhigh) from ambient measurements with calibration cells of 2.2×1017 and 2.2×1016 molec. cm−2 inserted in the light path at different viewing elevation angles using an Ocean Optics USB2000 spectrometer in a miniature MAX-DOAS instrument. SO2 dSCDs were the least accurate, and fit errors were highest for fitting windows with λlow < 307 or λlow > 312 nm. The SO2 dSCDs also exhibited an inverse relationship with the depth of the differential features in the SO2 absorption cross section for fitting windows with λlow < 307 nm. Spectra measured at low viewing elevation angles (i.e., α=2∘) exhibited less accurate SO2 dSCDs for the same fitting windows compared with higher angles. The use of a 400 nm short-pass filter or a polynomial to account for stray light (the offset function) increased the accuracy of the SO2 dSCDs for many different fitting windows, decreased fit errors, and decreased the dSCDs' dependence on the depth of the SO2 differential absorption features. These results suggest that the radiance at shorter wavelengths was increased by stray light. The inaccuracies at lower fitting wavelengths were increased by stray light originating from light with λ > 400 nm. Deviation of the SO2 dSCD from the true value depended on the SO2 concentration for some fitting windows rather than exhibiting a consistent bias. Uncertainties in the SO2 dSCD reported by the fit algorithm were more than 50 % less than the true error for many windows, particularly for the measurements without the filter or offset function. For retrievals with the filter or offset function, increasing λhigh > 320 nm tended to decrease the reported fit uncertainty but did not increase the accuracy. Based on the results of this study, a short-pass filter and a fitting window of 307.5 < λ < 319 nm are recommended for the retrieval of SO2 SCDs from miniature MAX-DOAS measurements. If a filter is not available or conflicts with other species to be determined (e.g., NO2 or HCHO), the offset function should be enabled, and a fit window 307.5 < λ < 319 nm is still recommended.

Validation of Aura-OMI QA4ECV NO<sub>2</sub> climate data records with ground-based DOAS networks: the role of measurement and comparison uncertainties

Abstract. The QA4ECV (Quality Assurance for Essential Climate Variables) version 1.1 stratospheric and tropospheric NO2 vertical column density (VCD) climate data records (CDRs) from the OMI (Ozone Monitoring Instrument) satellite sensor are validated using NDACC (Network for the Detection of Atmospheric Composition Change) zenith-scattered light differential optical absorption spectroscopy (ZSL-DOAS) and multi-axis DOAS (MAX-DOAS) data as a reference. The QA4ECV OMI stratospheric VCDs have a small bias of ∼0.2 Pmolec.cm-2 (5 %–10 %) and a dispersion of 0.2 to 1 Pmolec.cm-2 with respect to the ZSL-DOAS measurements. QA4ECV tropospheric VCD observations from OMI are restricted to near-cloud-free scenes, leading to a negative sampling bias (with respect to the unrestricted scene ensemble) of a few peta molecules per square centimetre (Pmolec.cm-2) up to −10 Pmolec.cm-2 (−40 %) in one extreme high-pollution case. The QA4ECV OMI tropospheric VCD has a negative bias with respect to the MAX-DOAS data (−1 to −4 Pmolec.cm-2), which is a feature also found for the OMI OMNO2 standard data product. The tropospheric VCD discrepancies between satellite measurements and ground-based data greatly exceed the combined measurement uncertainties. Depending on the site, part of the discrepancy can be attributed to a combination of comparison errors (notably horizontal smoothing difference error), measurement/retrieval errors related to clouds and aerosols, and the difference in vertical smoothing and a priori profile assumptions.

Comparison and Validation of TROPOMI and OMI NO2 Observations over China

The new-generation sensor TROPOspheric Monitoring Instrument (TROPOMI) onboard the Sentinel 5 precursor (S5P) satellite is promising for monitoring air pollutants with greater spatial resolution, especially for China, which suffers from severe pollution. As tropospheric NO2 vertical column densities (VCDs) from TROPOMI have become available since February 2018, this study presents the comparisons of NO2 data measured by TROPOMI and its predecessor Ozone Monitoring Instrument (OMI) over China, together with validation against ground Multi-axis differential optical absorption spectroscopy (MAX-DOAS) measurements. At the nationwide scale, we used two different filters performed for the TROPOMI data (named TROPOMI50 and TROPOMI75), and the TROPOMI50 yielded larger values than TROPOMI75. The TROPOMI NO2 datasets from different filters show consistent spatial patterns with OMI, and the correlation coefficient values were both above 0.93. However, linear regression indicates that NO2 loadings in TROPOMI is about 2/3 to 4/5 of those in OMI, which is presumably due to a different cloud mask and uncertainties of air mass factors. The absolute difference is prominent over the high pollution areas such as Jing-Jin-Ji region and during winter and autumn, exceeding 0.6 × 1016 molecules cm−2 (molec cm−2). However, the NO2 concentrations retrieved from TROPOMI50 in the southern China may be somewhat higher than OMI. When it comes to the local-scale Jing-Jin-Ji hotspot, the analysis focuses on a comparison to TROPOMI75. TROPOMI manifests high quality and exhibits a significantly better performance of representing spatial variability. In contrast, OMI shows fewer effective pixels and does a poor job of capturing local details due to its row anomaly and low resolution. The absolute difference between two datasets shows the same seasonal behavior with NO2 variation, which is most striking in the winter (0.31 × 1016 molec cm−2) and is lowest in the summer (0.05 × 1016 molec cm−2). Furthermore, the ground MAX-DOAS instrument in Xianghe station, the representative site in Jing-Jin-Ji, is used to assess the skill of satellite retrievals. It turns out that both OMI and TROPOMI underestimate the observations, ranging from 30% to 50%, with OMI being less biased. In spite of the negative drift, the temporal structures of changes derived from OMI and TROPOMI closely match the ground-based records, since the correlation coefficients are above 0.8 and 0.95 for daily and monthly scales, respectively. Overall, TROPOMI NO2 retrievals are better suited for applications in China as well as the Jing-Jin-Ji hotspot due to its higher spatial resolution, although some improvements are also needed in the near future.

MAX-DOAS measurements of NO<sub>2</sub>, SO<sub>2</sub>, HCHO, and BrO at the Mt. Waliguan WMO GAW global baseline station in the Tibetan Plateau

Abstract. Mt. Waliguan Observatory (WLG) is a World Meteorological Organization (WMO) Global Atmosphere Watch (GAW) global baseline station in China. WLG is located at the northeastern part of the Tibetan Plateau (36∘17′ N, 100∘54′ E, 3816 m a.s.l.) and is representative of the pristine atmosphere over the Eurasian continent. We made long-term ground-based multi-axis differential optical absorption spectroscopy (MAX-DOAS) measurements at WLG during the period 2012–2015. In this study, we retrieve the differential slant column densities (dSCDs) and estimate the tropospheric background mixing ratios of different trace gases, including NO2, SO2, HCHO, and BrO, using the measured spectra at WLG. Averaging of 10 original spectra is found to be an “optimum option” for reducing both the statistical error of the spectral retrieval and systematic errors in the analysis. The dSCDs of NO2, SO2, HCHO, and BrO under clear-sky and low-aerosol-load conditions are extracted from measured spectra at different elevation angles at WLG. By performing radiative transfer simulations with the model TRACY-2, we establish approximate relationships between the trace gas dSCDs at 1∘ elevation angle and the corresponding average tropospheric background volume mixing ratios. Mixing ratios of these trace gases in the lower troposphere over WLG are estimated to be in a range of about 7 ppt (January) to 100 ppt (May) for NO2, below 0.5 ppb for SO2, between 0.4 and 0.9 ppb for HCHO, and lower than 0.3 ppt for BrO. The chemical box model simulations constrained by the NO2 concentration from our MAX-DOAS measurements show that there is a little net ozone loss (−0.8 ppb d−1) for the free-tropospheric conditions and a little net ozone production (0.3 ppb d−1) for the boundary layer conditions over WLG during summertime. Our study provides valuable information and data sets for further investigating tropospheric chemistry in the background atmosphere and its links to anthropogenic activities.

Long-distance mobile MAX-DOAS observations of NO2 and SO2 over the North China Plain and identification of regional transport and power plant emissions

In this study, the spatiotemporal distribution of the NO2 and SO2 Vertical Columns Densities (VCDs) in the North China Plain (NCP) region was measured by long-distance mobile measurements using a mobile Multi-AXis Differential Optical Absorption Spectroscopy (MAX-DOAS) instrument. The mobile observations were performed in both summer (July 2017) and winter (January and February 2018) and the total driving mileage exceeded 3000 km. The concentrations of NO2 and SO2 in different seasons and areas were significantly different. During winter, serious NO2 and SO2 pollution was observed in northern Anhui Province, central Shandong Province, and the Beijing-Tianjin-Hebei Region. The evolution and transportation processes of three typical heavy pollution cases were discussed in detail. Combined with the Weather Research and Forecasting with Chemistry model simulated wind field information, the NO2 transportation flux from northern Jiangsu Province to northern Anhui Province is quantified as 7.12 kg s−1. Finally, we estimated the NO2 and SO2 emissions from the Dezhou and Hengshui power plants by plume cross section scanning and encircled observations, respectively. The NO2 and SO2 emission fluxes of the Dezhou Power Plant are 0.79 kg s−1 and 1.11 kg s−1, respectively, while the NO2 and SO2 emission fluxes of the Hengshui Power Plant are 0.12 kg s−1 and 0.36 kg s−1, respectively. This study quantitatively analyzed the transportation of atmospheric pollutants and power plant emissions, which is helpful for understanding the occurrence and evolution of pollution and is also useful for the government to introduce policies to protect and control the atmospheric environment.

Evaluation of the accuracy of the Sentinel-5 Precursor operational SO<sub>2</sub> products over China

The Sentinel-5 Precursor (S-5P) was launched into low earth orbit with a single payload TROPOspheric Monitoring Instrument (TROPOMI) on 13 October, 2017. TROPOMI is able to provide atmospheric composition observations including sulfur dioxide (SO2) daily and globally. It has a higher spatial resolution, specifically with a ground resolution of 7 km ×3.5 km in the nadir, than previous satellite instruments such as Ozone Monitoring Instrument (OMI, 13 km ×24 km) and Ozone Mapping and Profiler Suite (OMPS, 50 km ×50 km). The three types of S-5P operational SO2 products (offline (OFFL), Reprocessing (RPRO) and Near Real Time (NRTI)) are on basis of the differential optical absorption spectroscopy (DOAS) algorithm, and available from the S-5P Pre-Operations Data Hub. To evaluate these data, the results of OFFL are compared to the measurements obtained by ground-based Multi-Axis DOAS (MAX-DOAS) and China National Environmental Monitoring Center (CNEMC). We find that the S-5P operational SO2 products significantly overestimate SO2 concentrations over Northern China. Compared with four ground-based MAX-DOAS measurements in terms of the weekly average SO2 vertical column densities (VCDs), the S-5P operational SO2 products exhibit an overestimation of 61%−140%, with the correlation coefficient less than 0.5. The a priori SO2 profiles in S-5P operational products are from daily Tracer Model (TM5) simulations. SO2 surface concentrations are converted by the S-5P operational SO2 products and a priori SO2 profiles used in the retrievals. The correlation coefficient between the SO2 surface concentrations measured by CNEMC over Northern China and those from the S-5P operational products is higher than 0.5, and the S-5P operational products at these CNEMC sites show an overestimation of about 54.6% on average. In this study, the SO2 products (TROPOMI USTC SO2 products) are retrieved by the University of Science and Technology of China (USTC) with the optimal estimation algorithm (OE) from TROPOMI measurements, with the a priori SO2 profiles from monthly average GEOS-Chem simulations. The mean biases between the TROPOMI USTC SO2 products and the ground-based MAX-DOAS measurements are reduced significantly (−4.8%−22%), together with an improvement in the correlation coefficients (0.72−0.89). TROPOMI USTC SO2 surface concentrations are transformed by the TROPOMI USTC SO2 products and a priori SO2 profiles in the retrievals. Based on the evaluation statistics of the S-5P operational SO2 products, a smaller mean bias of −25.8% is found between the TROPOMI USTC SO2 surface concentrations and CNEMC measurements over Northern China. Compared to the TROPOMI USTC SO2 products in the heavily polluted area (33°−45°N, 110°−122°E), the S-5P operational SO2 products have an overestimation of around 41.3%, with a correlation coefficient of 0.73. In addition, S-5P operational SO2 products show a larger area of heavy pollution than TROPOMI USTC SO2 products. Additionally, the sensitivity analysis indicates many influential factors of the SO2 retrievals using OE algorithm, such as radiative calibration, fitting window and a priori SO2 profiles. In the fitting window of 310.5−326.0 nm, the SO2 columns retrieved by the a priori profiles from monthly GEOS-Chem simulations show better agreement with the MAX-DOAS measurements than those from daily TM5 simulations. A possible reason is that the emission inventory used in GEOS-Chem is based on a Chinese power sector database for 31 provinces supported by CMEP (Chinese Ministry of Environmental Protection), resulting in a better performance of GEOS-Chem than that of TM5 over China in simulations. And the overestimation of the S-5P operational SO2 products over Northern China may be attributed to the fitting window used.

Intercomparison of NO<sub>2</sub>, O<sub>4</sub>, O<sub>3</sub> and HCHO slant column measurements by MAX-DOAS and zenith-sky UV–visible spectrometers during CINDI-2

Abstract. In September 2016, 36 spectrometers from 24 institutes measured a number of key atmospheric pollutants for a period of 17 d during the Second Cabauw Intercomparison campaign for Nitrogen Dioxide measuring Instruments (CINDI-2) that took place at Cabauw, the Netherlands (51.97∘ N, 4.93∘ E). We report on the outcome of the formal semi-blind intercomparison exercise, which was held under the umbrella of the Network for the Detection of Atmospheric Composition Change (NDACC) and the European Space Agency (ESA). The three major goals of CINDI-2 were (1) to characterise and better understand the differences between a large number of multi-axis differential optical absorption spectroscopy (MAX-DOAS) and zenith-sky DOAS instruments and analysis methods, (2) to define a robust methodology for performance assessment of all participating instruments, and (3) to contribute to a harmonisation of the measurement settings and retrieval methods. This, in turn, creates the capability to produce consistent high-quality ground-based data sets, which are an essential requirement to generate reliable long-term measurement time series suitable for trend analysis and satellite data validation. The data products investigated during the semi-blind intercomparison are slant columns of nitrogen dioxide (NO2), the oxygen collision complex (O4) and ozone (O3) measured in the UV and visible wavelength region, formaldehyde (HCHO) in the UV spectral region, and NO2 in an additional (smaller) wavelength range in the visible region. The campaign design and implementation processes are discussed in detail including the measurement protocol, calibration procedures and slant column retrieval settings. Strong emphasis was put on the careful alignment and synchronisation of the measurement systems, resulting in a unique set of measurements made under highly comparable air mass conditions. The CINDI-2 data sets were investigated using a regression analysis of the slant columns measured by each instrument and for each of the target data products. The slope and intercept of the regression analysis respectively quantify the mean systematic bias and offset of the individual data sets against the selected reference (which is obtained from the median of either all data sets or a subset), and the rms error provides an estimate of the measurement noise or dispersion. These three criteria are examined and for each of the parameters and each of the data products, performance thresholds are set and applied to all the measurements. The approach presented here has been developed based on heritage from previous intercomparison exercises. It introduces a quantitative assessment of the consistency between all the participating instruments for the MAX-DOAS and zenith-sky DOAS techniques.

First observation of tropospheric nitrogen dioxide from the Environmental Trace Gases Monitoring Instrument onboard the GaoFen-5 satellite

The Environmental Trace Gases Monitoring Instrument (EMI) is the first Chinese satellite-borne UV–Vis spectrometer aiming to measure the distribution of atmospheric trace gases on a global scale. The EMI instrument onboard the GaoFen-5 satellite was launched on 9 May 2018. In this paper, we present the tropospheric nitrogen dioxide (NO2) vertical column density (VCD) retrieval algorithm dedicated to EMI measurement. We report the first successful retrieval of tropospheric NO2 VCD from the EMI instrument. Our retrieval improved the original EMI NO2 prototype algorithm by modifying the settings of the spectral fit and air mass factor calculations to account for the on-orbit instrumental performance changes. The retrieved EMI NO2 VCDs generally show good spatiotemporal agreement with the satellite-borne Ozone Monitoring Instrument and TROPOspheric Monitoring Instrument (correlation coefficient R of ~0.9, bias < 50%). A comparison with ground-based MAX-DOAS (Multi-Axis Differential Optical Absorption Spectroscopy) observations also shows good correlation with an R of 0.82. The results indicate that the EMI NO2 retrieval algorithm derives reliable and precise results, and this algorithm can feasibly produce stable operational products that can contribute to global air pollution monitoring.

A multi-axis differential optical absorption spectroscopy aerosol profile retrieval algorithm for high-altitude measurements: application to measurements at Schneefernerhaus (UFS), Germany

Abstract. We present a new aerosol extinction profile retrieval algorithm for multi-axis differential optical absorption spectrometer (MAX-DOAS) measurements at high-altitude sites. The algorithm is based on the lookup table method. It is applied to retrieve aerosol extinction profiles from the long-term MAX-DOAS measurements (February 2012 to February 2016) at the Environmental Research Station Schneefernerhaus (UFS), Germany (47.417∘ N, 10.980∘ E), which is located near the summit of Zugspitze at an altitude of 2650 m. The lookup table consists of simulated O4 differential slant column densities (DSCDs) corresponding to numerous possible aerosol extinction profiles. The sensitivities of O4 absorption to several parameters were investigated for the design and parameterization of the lookup table. In the retrieval, simulated O4 DSCDs for each possible profile are derived by interpolating the lookup table to the observation geometries. The cost functions are calculated for each aerosol profile in the lookup table based on the simulated O4 DSCDs, the O4 DSCD observations, and the measurement uncertainties. Valid profiles are selected from all the possible profiles according to the cost function, and the optimal solution is defined as the weighted mean of all the valid profiles. A comprehensive error analysis is performed to better estimate the total uncertainty. Based on the assumption that the lookup table covers all possible profiles under clear-sky conditions, we determined a set of O4 DSCD scaling factors for different elevation angles and wavelengths. The profiles retrieved from synthetic measurement data can reproduce the synthetic profile. The results also show that the retrieval is insensitive to measurement noise, indicating the retrieval is robust and stable. The aerosol optical depths (AODs) retrieved from the long-term measurements were compared to coinciding and co-located sun photometer observations. High correlation coefficients (R) of 0.733 and 0.798 are found for measurements at 360 and 477 nm, respectively. However, especially in summer, the sun photometer AODs are systematically higher than the MAX-DOAS retrievals by a factor of ∼2. The discrepancy might be related to the limited measurement range of the MAX-DOAS and is probably also related to the decreased sensitivity of the MAX-DOAS measurements at higher altitudes. The MAX-DOAS measurements indicate the aerosol extinction decreases with increasing altitude during all seasons, which agrees with the co-located ceilometer measurements. Our results also show maximum AOD and maximum Ångström exponent in summer, which is consistent with observations at an AERONET station located ∼43 km from the UFS.