Differential Slant Column Densities Research Articles

Retrieval of Tropospheric NO2 Vertical Column Densities from Ground-Based MAX-DOAS Measurements in Lhasa, a City on the Tibetan Plateau

In order to investigate the abundance of and temporal variation in nitrogen dioxide (NO2) in the troposphere and validate the corresponding satellite products during a normal year and the lockdown period of coronavirus disease 2019 (COVID-19) in Lhasa, a city on the Tibetan Plateau (TP), ground-based remote-sensing measurements captured by applying multi-axis differential optical absorption spectroscopy (MAX-DOAS) were recorded from August 2021 to March 2023 at the Lhasa site (91.14°E, 29.66°N; 3552.5 m altitude). The NO2 differential slant column densities (dSCDs) were retrieved from the spectra of scattered solar light at different elevation angles. Then, the tropospheric NO2 vertical column densities (VCDs) were calculated with the geometric approximation method. Based on the retrieved tropospheric NO2 VCDs, we found that the pattern of monthly variation in tropospheric NO2 VCDs in Lhasa presented two peaks, one in winter and one around May. According to the monthly means of tropospheric NO2 VCDs during the COVID-19 lockdown, the NO2 background level in Lhasa was estimated to be 0.53 × 1015 molecules·cm−2. For diurnal variations in tropospheric NO2 VCDs, the morning and evening peaks disappeared during the COVID-19 lockdown period. The east–west direction (i.e., along the river valley) was the main path of NO2 transport and dispersion in Lhasa, but the tropospheric NO2 VCDs were little dependent on the wind direction or wind speed during the COVID-19 lockdown. The correlation coefficient of tropospheric NO2 VCDs was R = 0.33 (R = 0.43), with the averaged relative deviation of −28% (99%) for the TROPOMI (GEMS) relative to ground-based MAX-DOAS. The monthly deviations of tropospheric NO2 VCDs between ground-based MAX-DOAS and the satellite showed a dependence on NO2 abundance, with the maxima of the monthly positive deviations during the COVID-19 lockdown period. The GEMS could not capture the strong and systematic diurnal variation in tropospheric NO2 VCDs in the “normal” year well. During the COVID-19 lockdown, the GEMS (>2 × 1015 molecules·cm−2) overestimated the hourly levels measured by ground-based MAX-DOAS (<1.6 × 1015 molecules·cm−2). As a whole, these results are beneficial to understanding the influences of anthropogenic activities on NO2 background levels in Lhasa and to learning the accuracy of satellite products over the TP, with its high altitude and complex terrain.

Study of atmospheric glyoxal using multiple axis differential optical spectroscopy (MAX-DOAS) in India

Glyoxal (CHOCHO) is an important atmospheric trace gas formed by the oxidation of volatile organic compounds (VOCs). We present a study of atmospheric CHOCHO from three locations (Pune, Mahabaleshwar and Delhi) in India using Multi-Axis Differential Optical Spectroscopy (MAX-DOAS) observations. Pune and Delhi represent urban environments, whereas Mahabaleshwar represents a forested rural region. Differential slant column densities (dSCDs), vertical column densities (VCDs), surface volume mixing ratios (vmr) and vertical profiles of CHOCHO were measured and compared to satellite observations. Delhi showed the highest average CHOCHO VCD (1.57 ± 0.98 × 1015 molec. cm−2) and vmr (average of 0.43 ± 0.27 ppb), whereas Mahabaleshwar showed the lowest average VCD (0.66 ± 0.40 × 1015 molec. cm−2) and average vmr (0.08 ± 0.03 ppb) among the three sites. Average CHOCHO VCD (1.52 ± 0.66 × 1015 molec. cm−2) and vmr (0.33 ± 0.18 ppb) over Pune were close to but lower than Delhi. A large seasonal variation was observed in Pune, with the highest (1.82 ± 0.62 × 1015 molec. cm−2) and lowest (0.79 ± 0.45 × 1015 molec. cm−2) monthly average VCDs observed in January and May, respectively. This inter-annual pattern was observed in both ground-based and satellite observations. Satellite observations systematically underestimated the CHOCHO VCDs compared to ground-based observations. Comparison with previous studies shows that Pune and Delhi have similar levels of CHOCHO with respect to other urban regions, while Mahabaleshwar is comparable to other remote environments worldwide.

Mobile MAX-DOAS observations of tropospheric NO2 and HCHO during summer over the Three Rivers' Source region in China

Abstract. The tropospheric concentrations of nitrogen dioxide (NO2) and formaldehyde (HCHO) have high spatio-temporal variability, and in situ observations of these trace gases are still scarce, especially in remote background areas. We made four similar circling journeys of mobile multi-axis differential optical absorption spectroscopy (MAX-DOAS) measurements in the Three Rivers' Source region over the Tibetan Plateau in summer (18–30 July) 2021 for the first time. The differential slant column densities (DSCDs) of NO2 and HCHO were retrieved from the measured spectra, with very weak absorptions along the driving routes. The tropospheric NO2 and HCHO vertical column densities (VCDs) were calculated from their DSCDs by the geometric approximation method, and they were further filtered to form reliable data sets by eliminating the influences of sunlight shelters and the vehicle's vibration and bumpiness. The observational data show that the tropospheric NO2 and HCHO VCDs decreased with the increasing altitude of the driving route, whose background levels ± standard deviations were 0.40 ± 1.13×1015 molec. cm−2 for NO2 and 2.27±1.66×1015 molec. cm−2 for HCHO in July 2021 over the Three Rivers' Source region. The NO2 VCDs show similar geographical distribution patterns between the different circling journeys, but the levels of the HCHO VCDs are different between the different circling journeys. The elevated NO2 VCDs along the driving routes usually corresponded to enhanced transport emissions from the towns crossed. However, the spatial distributions of the HCHO VCDs depended significantly on natural and meteorological conditions, such as surface temperature. By comparing TROPOMI satellite products and mobile MAX-DOAS results, we found that TROPOMI NO2 and HCHO VCDs have large positive offsets in the background atmosphere over the main area of the Three Rivers' Source. Our study provides valuable data sets and information of NO2 and HCHO over the Tibetan Plateau, benefitting the scientific community in investigating the spatio-temporal evolution of atmospheric composition in the background atmosphere at high altitudes, validating and improving the satellite products over mountain terrains, and evaluating the model's ability to simulate atmospheric chemistry over the Tibetan Plateau.

Retrieval of tropospheric ozone profiles using ground-based MAX-DOAS.

In recent years, surface ozone concentrations have increased in many cities in China. Ground-based multi-axis differential optical absorption spectroscopy (MAX-DOAS) is a powerful technique for retrieving the profiles of tropospheric trace gases, such as NO2, SO2, and HCHO. However, since the difficulties in deducting the effects of stratospheric ozone, there are few studies on the retrieval of tropospheric ozone profiles using MAX-DOAS measurements. Here, we developed an accurate inversion method to retrieve tropospheric ozone concentrations during the PRIDE-GBA Campaign, wherein the ozone differential slant column densities (DSCDs) were retrieved in QDOAS software using the "time-interpolated zenith spectrum" as the reference spectrum. The tropospheric DSCDs (DSCDstrop) were then calculated by subtracting the simulated stratospheric DSCDs (DSCDsstr, simulated from the SCIATRAN model) from the DSCDs. Tropospheric ozone profiles were retrieved from the DSCDstrop using the optimal estimation method (OEM). The results showed that high values of tropospheric ozone were mainly distributed below 1 km, which is consistent with lidar measurements. In addition, the observed surface ozone concentrations were highly correlated with the in-situ measurements, with correlation coefficients (R) of 0.75 and 0.81, respectively. Combined with the retrieved NO2 and HCHO profiles using the MAX-DOAS measurements, we found that the planetary boundary layer ozone pollution of HeShan Observatory during the PRIDE-GBA Campaign are controlled by the NOx-limited regime. The results of this study indicate that the MAX-DOAS technique has the potential to retrieve tropospheric ozone profiles with high temporal and spatial resolution.

Retrieval of tropospheric aerosol, NO<sub>2</sub>, and HCHO vertical profiles from MAX-DOAS observations over Thessaloniki, Greece: intercomparison and validation of two inversion algorithms

Abstract. In this study we focus on the retrieval of aerosol and trace gas vertical profiles from multi-axis differential optical absorption spectroscopy (MAX-DOAS) observations for the first time over Thessaloniki, Greece. We use two independent inversion algorithms for the profile retrievals: the Mexican MAX-DOAS Fit (MMF) and the Mainz Profile Algorithm (MAPA). The former is based on the optimal estimation method (OEM), while the latter follows a parameterization approach. We evaluate the performance of MMF and MAPA, and we validate their retrieved products with ancillary data measured by other co-located reference instruments. The trace gas differential slant column densities (dSCDs), simulated by the forward models, are in good agreement, except for HCHO, where larger scatter is observed due to the increased spectral noise of the measurements in the UV. We find an excellent agreement between the tropospheric column densities of NO2 retrieved by MMF and MAPA (slope=1.009, Pearson's correlation coefficient R=0.982) and a good correlation for the case of HCHO (R=0.927). For aerosols, we find better agreement for the aerosol optical depths (AODs) in the visible (i.e., at 477 nm) compared to the UV (at 360 nm), and we show that the agreement strongly depends on the O4 scaling factor that is used in the analysis. The agreement for NO2 and HCHO near-surface concentrations is similar to the comparison of the integrated columns with slightly decreased correlation coefficients. The seasonal mean vertical profiles that are retrieved by MMF and MAPA are intercompared, and the seasonal variation in all species along with possible sources is discussed. The AODs retrieved by the MAX-DOAS are validated by comparing them with AOD values measured by a CIMEL sun photometer and a Brewer spectrophotometer. Four different flagging schemes were applied to the data in order to evaluate their performance. Qualitatively, a generally good agreement is observed for both wavelengths, but we find a systematic bias from the CIMEL sun photometer and Brewer spectrophotometer measurements, due to the limited sensitivity of the MAX-DOAS in retrieving information at higher altitudes, especially in the UV. An in-depth validation of the aerosol vertical profiles retrieved by the MAX-DOAS is not possible since only in very few cases is the true aerosol profile known during the period of study. However, we examine four cases, where the MAX-DOAS provided a generally good estimation of the shape of the profiles retrieved by a co-located multi-wavelength lidar system. The NO2 near-surface concentrations are validated against in situ observations, and the comparison of both MMF and MAPA revealed good agreement with correlation coefficients of R=0.78 and R=0.73, respectively. Finally, the effect of the O4 scaling factor is investigated by intercomparing the integrated columns retrieved by the two algorithms and also by comparing the AODs derived by MAPA for different values of the scaling factor with AODs measured by the CIMEL sun photometer and the Brewer spectrophotometer.

Retrieval of O3, NO2, BrO and OClO Columns from Ground-Based Zenith Scattered Light DOAS Measurements in Summer and Autumn over the Northern Tibetan Plateau

Ground-based zenith scattered light differential optical absorption spectroscopy (DOAS) measurements were performed in summer and autumn (27 May–30 November) 2020 at Golmud (94°54′ E, 36°25′ N; 2807.6 m altitude) to investigate the abundances and temporal variations of ozone (O3) and its depleting substances over the northern Tibetan Plateau (TP). The differential slant column densities (dSCDs) of O3, nitrogen dioxide (NO2), bromine monoxide (BrO), and chlorine dioxide (OClO) were simultaneously retrieved from scattered solar spectra in the zenith direction during the twilight period. The O3 vertical column densities (VCDs) were derived by applying the Langley plot method, for which we investigated the sensitivities to the chosen wavelength, the a-priori O3 profile and the aerosol extinction profile used in O3 air mass factor (AMF) simulation as well as the selected solar zenith angle (SZA) range. The mean O3 VCDs from June to November 2020 are 7.21 × 1018 molec·cm−2 and 7.18 × 1018 molec·cm−2 at sunrise and sunset, respectively. The derived monthly variations of the O3 VCDs, ranging from a minimum of 6.9 × 1018 molec·cm−2 in October to 7.5 × 1018 molec·cm−2 in November, well matched the OMI satellite product, with a correlation coefficient R = 0.98. The NO2 VCDs at SZA = 90°, calculated by a modified Langley plot method, were systematically larger at sunset than at sunrise as expected with a pm/am ratio of ~1.56. The maximum of the monthly NO2 VCDs, averaged between sunrise and sunset, was 3.40 × 1015 molec·cm−2 in July. The overall trends of the NO2 VCDs were gradually decreasing with the time and similarly observed by the ground-based zenith DOAS and OMI. The average level of the BrO dSCD90°–80° (i.e., dSCD between 90° and 80° SZA) was 2.06 × 1014 molec·cm−2 during the period of June–November 2020. The monthly BrO dSCD90°–80° presented peaks in August and July for sunrise and sunset, respectively, and slowly increased after October. During the whole campaign period, the OClO abundance was lower than the detection limit of the instrument. This was to be expected because during that season the stratospheric temperatures were above the formation temperature of polar stratospheric clouds. Nevertheless, this finding is still of importance, because it indicates that the OClO analysis works well and is ready to be used during periods when enhanced OClO abundances can be expected. As a whole, ground-based zenith DOAS observations can serve as an effective way to measure the columns of O3 and its depleting substances over the TP. The aforementioned results are helpful in investigating stratospheric O3 chemistry over the third pole of the world.

Evaluation of the coupled high-resolution atmospheric chemistry model system MECO(n) using in situ and MAX-DOAS NO<sub>2</sub> 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.

Research of NO2 vertical profiles with look-up table method based on MAX-DOAS

Obtaining the vertical distribution profile of trace gas is of great significance for studying the diffusion procedure of air pollution. In this article, a look-up table method based on multi-axis differential optical absorption spectroscopy (MAXDOAS) technology is established for retrieving the tropospheric NO2 vertical distribution profiles. This method retrieves the aerosol extinction profiles with minimum cost function. Then, the aerosol extinction profiles and the atmospheric radiation transfer model (RTM) are employed to establish the look-up table for retrieving the NO2 vertical column densities (VCDs) and profiles. The measured NO2 differential slant column densities (DSCDs) are compared with the NO2 DSCDs simulated by the atmospheric RTM, and the NO2 VCDs, the weight factor of NO2 in the boundary layer, and the boundary layer height are obtained by the minimization process. The look-up table is established to retrieve NO2 VCDs based on MAX-DOAS measurements in Huaibei area, and the results are compared with the data from Copernicus Atmospheric Monitoring Service(CAMS) model. It isfound that there are nearly consistent and the correlation coefficient R2 is morethan 0.86. The results show that this technology provides a more convenient and accurate retrieval method for the stereoscopic monitoring ofatmospheric environment.

Recommendations for HCHO and SO2 Retrieval Settings from MAX-DOAS Observations under Different Meteorological Conditions

Recently, the occurrence of fog and haze over China has increased. The retrieval of trace gases from the multi-axis differential optical absorption spectroscopy (MAX-DOAS) is challenging under these conditions. In this study, various reported retrieval settings for formaldehyde (HCHO) and sulfur dioxide (SO2) are compared to evaluate the performance of these settings under different meteorological conditions (clear day, haze, and fog). The dataset from 1st December 2019 to 31st March 2020 over Nanjing, China, is used in this study. The results indicated that for HCHO, the optimal settings were in the 324.5–359 nm wavelength window with a polynomial order of five. At these settings, the fitting and root mean squared (RMS) errors for column density were considerably improved for haze and fog conditions, and the differential slant column densities (DSCDs) showed more accurate values compared to the DSCDs between 336.5 and 359 nm. For SO2, the optimal settings for retrieval were found to be at 307–328 nm with a polynomial order of five. Here, root mean square (RMS) and fitting errors were significantly lower under all conditions. The observed HCHO and SO2 vertical column densities were significantly lower on fog days compared to clear days, reflecting a decreased chemical production of HCHO and aqueous phase oxidation of SO2 in fog droplets.

Effect of Polyoxymethylene (POM-H Delrin) offgassing within Pandora head sensor on direct sun and multi-axis formaldehyde column measurements in 2016 - 2019.

Analysis of formaldehyde measurements by the Pandora spectrometer systems between 2016 and 2019 suggested that there was a temperature dependent process inside Pandora head sensor that emitted formaldehyde. Some parts in the head sensor were manufactured from thermal plastic polyoxymethylene homopolimer (E.I. Du Pont de Nemour & Co., USA: POM-H Delrin®) and were responsible for formaldehyde production. Laboratory analysis of the four Pandora head sensors showed that internal formaldehyde production had exponential temperature dependence with a damping coefficient of 0.0911±0.0024 °C-1 and the exponential function amplitude ranging from 0.0041 DU to 0.049 DU. No apparent dependency on the head sensor age and heating/cooling rates was detected. The total amount of formaldehyde internally generated by the POM-H Delrin components and contributing to the direct sun measurements were estimated based on the head sensor temperature and solar zenith angle of the measurements. Measurements in winter, during colder (<10°C) days in general and at high solar zenith angles (> 75 °) were minimally impacted. Measurements during hot days (>28°C) and small solar zenith angles had up to 1 DU (2.69×1016 molecules/cm2) contribution from POM-H Delrin parts. Multi-axis differential slant column densities were minimally impacted (< 0.01 DU) due to the reference spectrum collected within a short time period with a small difference in head sensor temperature. Three new POM-H Delrin free Pandora head sensors (manufactured in summer 2019) were evaluated for temperature dependent attenuation across the entire spectral range (300 to 530 nm). No formaldehyde or any other absorption above the instrumental noise was observed across the entire spectral range.

Formaldehyde total column densities over Mexico City: comparison between multi-axis differential optical absorption spectroscopy and solar-absorption Fourier transform infrared measurements

Abstract. Formaldehyde (HCHO) total column densities over the Mexico City metropolitan area (MCMA) were retrieved using two independent measurement techniques: multi-axis differential optical absorption spectroscopy (MAX-DOAS) and Fourier transform infrared (FTIR) spectroscopy. For the MAX-DOAS measurements, the software QDOAS was used to calculate differential slant column densities (dSCDs) from the measured spectra and subsequently the Mexican MAX-DOAS fit (MMF) retrieval code to convert from dSCDs to vertical column densities (VCDs). The direct solar-absorption spectra measured with FTIR were analyzed using the PROFFIT (PROFile FIT) retrieval code. Typically the MAX-DOAS instrument reports higher VCDs than those measured with FTIR, in part due to differences found in the ground-level sensitivities as revealed from the retrieval diagnostics from both instruments, as the FTIR and the MAX-DOAS information do not refer exactly to the same altitudes of the atmosphere. Three MAX-DOAS datasets using measurements conducted towards the east, west or both sides of the measurement plane were evaluated with respect to the FTIR results. The retrieved MAX-DOAS HCHO VCDs where 6 %, 8 % and 28 % larger than the FTIR measurements which, supported with satellite data, indicates a large horizontal inhomogeneity in the HCHO abundances. The temporal change in the vertical distribution of this pollutant, guided by the evolution of the mixing-layer height, affects the comparison of the two retrievals with different sensitivities (total column averaging kernels). In addition to the reported seasonal and diurnal variability of HCHO columns within the urban site, background data from measurements at a high-altitude station, located only 60 km away, are presented.

Intercomparison of MAX-DOAS vertical profile retrieval algorithms: studies on field data from the CINDI-2 campaign

Abstract. The second Cabauw Intercomparison of Nitrogen Dioxide measuring Instruments (CINDI-2) took place in Cabauw (the Netherlands) in September 2016 with the aim of assessing the consistency of multi-axis differential optical absorption spectroscopy (MAX-DOAS) measurements of tropospheric species (NO2, HCHO, O3, HONO, CHOCHO and O4). This was achieved through the coordinated operation of 36 spectrometers operated by 24 groups from all over the world, together with a wide range of supporting reference observations (in situ analysers, balloon sondes, lidars, long-path DOAS, direct-sun DOAS, Sun photometer and meteorological instruments). In the presented study, the retrieved CINDI-2 MAX-DOAS trace gas (NO2, HCHO) and aerosol vertical profiles of 15 participating groups using different inversion algorithms are compared and validated against the colocated supporting observations, with the focus on aerosol optical thicknesses (AOTs), trace gas vertical column densities (VCDs) and trace gas surface concentrations. The algorithms are based on three different techniques: six use the optimal estimation method, two use a parameterized approach and one algorithm relies on simplified radiative transport assumptions and analytical calculations. To assess the agreement among the inversion algorithms independent of inconsistencies in the trace gas slant column density acquisition, participants applied their inversion to a common set of slant columns. Further, important settings like the retrieval grid, profiles of O3, temperature and pressure as well as aerosol optical properties and a priori assumptions (for optimal estimation algorithms) have been prescribed to reduce possible sources of discrepancies. The profiling results were found to be in good qualitative agreement: most participants obtained the same features in the retrieved vertical trace gas and aerosol distributions; however, these are sometimes at different altitudes and of different magnitudes. Under clear-sky conditions, the root-mean-square differences (RMSDs) among the results of individual participants are in the range of 0.01–0.1 for AOTs, (1.5–15) ×1014molec.cm-2 for trace gas (NO2, HCHO) VCDs and (0.3–8)×1010molec.cm-3 for trace gas surface concentrations. These values compare to approximate average optical thicknesses of 0.3, trace gas vertical columns of 90×1014molec.cm-2 and trace gas surface concentrations of 11×1010molec.cm-3 observed over the campaign period. The discrepancies originate from differences in the applied techniques, the exact implementation of the algorithms and the user-defined settings that were not prescribed. For the comparison against supporting observations, the RMSDs increase to a range of 0.02–0.2 against AOTs from the Sun photometer, (11–55)×1014molec.cm-2 against trace gas VCDs from direct-sun DOAS observations and (0.8–9)×1010molec.cm-3 against surface concentrations from the long-path DOAS instrument. This increase in RMSDs is most likely caused by uncertainties in the supporting data, spatiotemporal mismatch among the observations and simplified assumptions particularly on aerosol optical properties made for the MAX-DOAS retrieval. As a side investigation, the comparison was repeated with the participants retrieving profiles from their own differential slant column densities (dSCDs) acquired during the campaign. In this case, the consistency among the participants degrades by about 30 % for AOTs, by 180 % (40 %) for HCHO (NO2) VCDs and by 90 % (20 %) for HCHO (NO2) surface concentrations. In former publications and also during this comparison study, it was found that MAX-DOAS vertically integrated aerosol extinction coefficient profiles systematically underestimate the AOT observed by the Sun photometer. For the first time, it is quantitatively shown that for optimal estimation algorithms this can be largely explained and compensated by considering biases arising from the reduced sensitivity of MAX-DOAS observations to higher altitudes and associated a priori assumptions.

Recommendations for spectral fitting of SO&amp;lt;sub&amp;gt;2&amp;lt;/sub&amp;gt; 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 &lt; 307 or λlow &gt; 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 &lt; 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 &gt; 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 &gt; 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 &lt; λ &lt; 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 &lt; λ &lt; 319 nm is still recommended.

MAX-DOAS measurements of NO&amp;lt;sub&amp;gt;2&amp;lt;/sub&amp;gt;, SO&amp;lt;sub&amp;gt;2&amp;lt;/sub&amp;gt;, 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.

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.

Observations of Atmospheric NO2 Using a New Low-Cost MAX-DOAS System

This article describes the prototype of a new MAX-DOAS (multi-axis differential optical absorption spectroscopy) system built at “Dunarea de Jos” University of Galati (UGAL), Romania, and the first results of its use to observe NO2 content over Galati city (45.42° N, 28.04° E). The new equipment is a ground-based MAX-DOAS system capable of measuring the spatial distribution of DSCD (differential slant column densities) of several trace gases using horizontal and vertical observations. The new optic system, named UGAL-2-DOAS, is an in-house, low-cost, solution in comparison to the existing market of the MAX-DOAS systems. This paper describes the technical design and capabilities of the new MAX-DOAS instrument. The UGAL-2D-DOAS system was tested in April and June 2017 in Galati city. Measurements over three days were selected for the present manuscript. Full azimuthal (0–360°), local celestial meridian observations and other elevation angle sequence measurements (e.g., E–W) were performed. We found that the new MAX-DOAS system is able to detect diurnal variation and the local source emissions of NO2 from the urban environment. Also, we present concomitant zenith-sky car-DOAS observations measurements around the location of the new MAX-DOAS instrument. Comparing the horizontal scanning sequence of the new developed instrument with the mobile DOAS observations, we found that both systems can indicate and detect the same NO2 sources.

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.

A new method to determine the aerosol optical properties from multiple-wavelength O&amp;lt;sub&amp;gt;4&amp;lt;/sub&amp;gt; absorptions by MAX-DOAS observation

Abstract. Ground-based multi-axis differential optical absorption spectroscopy (MAX-DOAS) observation was carried out from November 2016 to February 2017 in Beijing, China, to measure the O4 absorptions in UV and visible bands and further to illustrate its relationship with aerosol optical properties (AOPs) under different weather types. According to relative humidity, visibility, and PM2.5, we classified the observation periods into clear, light-haze, haze, heavy-haze, fog, and rainy weather conditions. There are obvious differences for measured AOPs under different weather conditions, especially scattering coefficient (σsca) and absorption coefficient (σsca). It was also found that both the O4 differential slant column densities (DSCDs) at the UV and visible bands varied in the order of clear days &gt; light-haze days &gt; haze days &gt; heavy-haze days &gt; fog days. The correlation coefficients (R2) between O4 DSCDs at 360.8 and 477.1 nm mainly varied in the order of clear days &gt; light-haze days &gt; haze days &gt; heavy-haze days. Based on the statistics of O4 DSCDs at an elevation angle 1∘ with the corresponding linear regression between UV and visible bands of segmental periods, the relationships between O4 DSCDs and AOPs were established. It should mainly be clear or light-haze days when the correlation slope is greater than 1.0, with a correlation coefficient (R2) greater than 0.9, and O4 DSCDs mainly greater than 2.5×1043 molec. cm−2. Meanwhile, σsca and σabs are less than 45 and 12 Mm−1, respectively. For haze or heavy-haze days, the correlation slope is less than 0.6, with an R2 less than 0.8, and O4 DSCDs mainly less than 1.3×1043 molec. cm−2, under which σsca and σabs are mainly located at 200–900 and 20–60 Mm−1. Additionally, the determination method was well validated based on another MAX-DOAS measurement at Gucheng from 19 to 27 November 2016. For more precise and accurate inversion of AOPs, more detailed look-up tables for O4 multiple-wavelength absorptions need to be developed. Since the ground surface AOPs were determined using MAX-DOAS observation at a 1∘ elevation in this study, we hope to highlight the potential of retrieved vertical spatially resolved AOPs being expected when multiple elevation angles of MAX-DOAS observation are used together.

NO&amp;lt;sub&amp;gt;2&amp;lt;/sub&amp;gt; vertical profiles and column densities from MAX-DOAS measurements in Mexico City

Abstract. We present a new numerical code, Mexican MAX-DOAS Fit (MMF), developed to retrieve profiles of different trace gases from the network of MAX-DOAS instruments operated in Mexico City. MMF uses differential slant column densities (dSCDs) retrieved with the QDOAS (Danckaert et al., 2013) software. The retrieval is comprised of two steps, an aerosol retrieval and a trace gas retrieval that uses the retrieved aerosol profile in the forward model for the trace gas. For forward model simulations, VLIDORT is used (e.g., Spurr et al., 2001; Spurr, 2006, 2013). Both steps use constrained least-square fitting, but the aerosol retrieval uses Tikhonov regularization and the trace gas retrieval optimal estimation. Aerosol optical depth and scattering properties from the AERONET database, averaged ceilometer data, WRF-Chem model data, and temperature and pressure sounding data are used for different steps in the retrieval chain. The MMF code was applied to retrieve NO2 profiles with 2 degrees of freedom (DOF = 2) from spectra of the MAX-DOAS instrument located at the Universidad Nacional Autónoma de México (UNAM) campus. We describe the full error analysis of the retrievals and include a sensitivity exercise to quantify the contribution of the uncertainties in the aerosol extinction profiles to the total error. A data set comprised of measurements from January 2015 to July 2016 was processed and the results compared to independent surface measurements. We concentrate on the analysis of four single days and additionally present diurnal and annual variabilities from averaging the 1.5 years of data. The total error, depending on the exact counting, is 14 %–20 % and this work provides new and relevant information about NO2 in the boundary layer of Mexico City.

Novel infrared differential optical absorption spectroscopy remote sensing system to measure carbon dioxide emission**Project supported by the Key Program of the National Natural Science Foundation of China (Grant No. 41530644).

A CO2 infrared remote sensing system based on the algorithm of weighting function modified differential optical absorption spectroscopy (WFM-DOAS) is developed for measuring CO2 emissions from pollution sources. The system is composed of a spectrometer with band from 900 nm to 1700 nm, a telescope with a field of view of 1.12°, a silica optical fiber, an automatic position adjuster, and the data acquisition and processing module. The performance is discussed, including the electronic noise of the charge-coupled device (CCD), the spectral shift, and detection limits. The resolution of the spectrometer is 0.4 nm, the detection limit is 8.5 × 1020 molecules·cm−2, and the relative retrieval error is < 1.5%. On May 26, 2018, a field experiment was performed to measure CO2 emissions from the Feng-tai power plant, and a two-dimensional distribution of CO2 from the plume was obtained. The retrieved differential slant column densities (dSCDs) of CO2 are around 2 × 1021 molecules·cm−2 in the unpolluted areas, 5.5 × 1021 molecules·cm−2 in the plume locations most strongly affected by local CO2 emissions, and the fitting error is less than 2 × 1020 molecules·cm−2, which proves that the infrared remote sensing system has the characteristics of fast response and high precision, suitable for measuring CO2 emission from the sources.