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Masaya volcano (Nicaragua, 12.0° N, 86.2° W, 635 m a.s.l.) is one of the few volcanoes hosting a lava lake, today. We present continuous time series of SO2 emission fluxes and BrO / SO2 molar ratios in the gas plume of Masaya from March 2014 to March 2020. This study has two foci: (1) discussing the state of the art of long-term SO2 emission flux monitoring on the example of Masaya and (2) the provision and discussion of a continuous dataset on volcanic gas data unique in its temporal coverage, which poses a major extension of the empirical data base for studies on the volcanologic as well as atmospheric bromine chemistry. Our SO2 emission flux retrieval is based on a comprehensive investigation of various aspects of the spectroscopic retrievals, the wind conditions, and the plume height. Our retrieved SO2 emission fluxes are on average a factor of 1.4 larger than former estimates based on the same data. We furthermore observed a correlation between the SO2 emission fluxes and the wind speed when several of our retrieval extensions are not applied. We make plausible that such a correlation is not expected and present a partial correction of this artefact via applying dynamic estimates for the plume height as a function of the wind speed (resulting in a vanishing correlation for wind speeds larger than 10 m/s). Our empirical data set covers the three time periods (1) before the lava lake elevation, (2) period of high lava lake activity (December 2015–May 2018), (3) after the period of high lava lake activity. For these three time periods, we report average SO2 emission fluxes of 1000 ± 200 t d−1, 1000 ± 300 t d−1, and 700 ± 200 t d−1 and average BrO / SO2 molar ratios of (2.9 ± 1.5) × 10−5, (4.8 ± 1 : 9) ×10−5, and (5.5 ± 2–6) × 10−5. These variations indicate that the two gas proxies provide complementary information: the BrO / SO2 molar ratios were susceptible in particular for the transition between the two former periods while the SO2 emission fluxes were in particular susceptible for the transition between the two latter time periods. We observed an extremely significant annual cyclicity for the BrO / SO2 molar ratios (amplitudes between 1–4–2–6 × 10−5) with a weak semi-annual modulation. We suggest that this cyclicity might be a manifestation of meteorological cycles. We found an anti-correlation between the BrO / SO2 molar ratios and the atmospheric water concentration (correlation coefficient of −47 %) but in contrast to that neither a correlation with the ozone mixing ratio (+21 %) nor systematic dependencies between the BrO / SO2 molar ratios and the atmospheric plume age for an age range of 2–20 min after the release from the volcanic edifice. The two latter observations indicate an early stop of the autocatalytic partial transformation of bromide Br− solved in aerosol particles to atmospheric BrO. Further patterns in the BrO / SO2 time series were (1) a step increase by 0.7 × 10−5 in late 2015, (2) a linear trend of 1.2 × 10−5 per year from December 2015 to March 2018, and (3) a linear trend of −0.8 × 10−5 per year from June 2018 to March 2020. The step increase in 2015 coincided with the 55 elevation of the lava lake and was thus most likely caused by a change in the magmatic system. The linear trend between late 2015 and early 2018 may indicate the evolution of the magmatic gas phase during the ascent of juvenile gas-rich magma whereas the linear trend from June 2018 on may indicate a decreasing bromine abundance in the magma.

In this study we compare measured and simulated O4 absorptions for conditions of extremely low aerosol optical depth (between 0.034 to 0.056 at 360 nm) on one day during a ship cruise in the tropical Atlantic. For such conditions, the uncertainties related to imperfect knowledge of aerosol properties don't significantly affect the comparison results. We find that the simulations underestimate the measurements by 15 % to 20 %. Even for simulations without any aerosols the measured O4 absorptions are still systematically higher than the simulation results. The observed discrepancies can not be explained by uncertainties of the measurements and simulations and thus indicate a fundamental inconsistency between simulations and measurements.

We present comprehensive long-term ground-based multi-axis differential optical absorption spectroscopy (MAX-DOAS) measurements of aerosols, nitrogen dioxide (NO2), and formaldehyde (HCHO) from Mohali (30.667∘ N, 76.739∘ E; ∼310 m above mean sea level), located in the densely populated Indo-Gangetic Plain (IGP) of India. We investigate the temporal variation in tropospheric columns, surface volume mixing ratio (VMR), and vertical profiles of aerosols, NO2, and HCHO and identify factors driving their ambient levels and distributions for the period from January 2013 to June 2017. We observed mean aerosol optical depth (AOD) at 360 nm, tropospheric NO2 vertical column density (VCD), and tropospheric HCHO VCD for the measurement period to be 0.63 ± 0.51, (6.7 ± 4.1) × 1015, and (12.1 ± 7.5) × 1015 molecules cm−2, respectively. Concerning the tropospheric NO2 VCDs, Mohali was found to be less polluted than urban and suburban locations of China and western countries, but comparable HCHO VCDs were observed. For the more than 4 years of measurements during which the region around the measurement location underwent significant urban development, we did not observe obvious annual trends in AOD, NO2, and HCHO. High tropospheric NO2 VCDs were observed in periods with enhanced biomass and biofuel combustion (e.g. agricultural residue burning and domestic burning for heating). Highest tropospheric HCHO VCDs were observed in agricultural residue burning periods with favourable meteorological conditions for photochemical formation, which in previous studies have shown an implication for high ambient ozone also over the IGP. Highest AOD is observed in the monsoon season, indicating possible hygroscopic growth of the aerosol particles. Most of the NO2 is located close to the surface, whereas significant HCHO is present at higher altitudes up to 600 m during summer indicating active photochemistry at high altitudes. The vertical distribution of aerosol, NO2, and HCHO follows the change in boundary layer height (BLH), from the ERA5 dataset of European Centre for Medium-Range Weather Forecasts, between summer and winter. However, deep convection during the monsoon transports the pollutants at high altitudes similar to summer despite a shallow ERA5 BLH. Strong gradients in the vertical profiles of HCHO are observed during the months when primary anthropogenic sources dominate the formaldehyde production. High-resolution MODIS AOD measurements correlate well but were systematically higher than MAX-DOAS AODs. The ground-based MAX-DOAS measurements were used to evaluate three NO2 data products and two HCHO data products of the Ozone Monitoring Instrument (OMI) for the first time over India and the IGP. NO2 VCDs from OMI correlate reasonably with MAX-DOAS VCDs but are lower by ∼30 %–50 % due to the difference in vertical sensitivities and the rather large OMI footprint. OMI HCHO VCDs exceed the MAX-DOAS VCDs by up to 30 %. We show that there is significant scope for improvement in the a priori vertical profiles of trace gases, which are used in OMI retrievals. The difference in vertical representativeness was found to be crucial for the observed biases in NO2 and HCHO surface VMR intercomparisons. Using the ratio of NO2 and HCHO VCDs measured from MAX-DOAS, we have found that the peak daytime ozone production regime is sensitive to both NOx and VOCs in winter but strongly sensitive to NOx in other seasons.

In this study the consistency between MAX-DOAS measurements and radiative transfer simulations of the atmospheric O4 absorption is investigated on 2 mainly cloud-free days during the MAD-CAT campaign in Mainz, Germany, in summer 2013. In recent years several studies indicated that measurements and radiative transfer simulations of the atmospheric O4 absorption can only be brought into agreement if a so-called scaling factor (

A multi-axis differential optical absorption spectroscopy (MAX-DOAS) instrument was deployed in May and June 2016 at a monitoring station (37.18 ∘ N, 114.36 ∘ E) in the suburban area of Xingtai, which is one of the most polluted cities in the North China Plain (NCP), during the Atmosphere-Aerosol-Boundary Layer-Cloud (A 2 BC) experiment and Air chemistry Research In Asia (ARIAs) joint experiments to derive tropospheric vertical profiles of NO2 , SO2 , HONO, HCHO, CHOCHO and aerosols. Aerosol optical depths derived from MAX-DOAS were found to be consistent with collocated sun-photometer measurements. Also the derived near-surface aerosol extinction and HCHO mixing ratio agree well with the coincident visibility meter and in situ HCHO measurements, with mean HCHO near-surface mixing ratios of ∼3.5 ppb. Underestimations of MAX-DOAS results compared to in situ measurements of NO2 ( ∼60 %) and SO2 ( ∼20 %) are found expectedly due to vertical and horizontal inhomogeneity of trace gases. Vertical profiles of aerosols and NO2 and SO2 are reasonably consistent with those measured by a collocated Raman lidar and aircraft spirals over the station. The deviations can be attributed to differences in sensitivity as a function of altitude and substantial horizontal gradients of pollutants. Aerosols, HCHO and CHOCHO profiles typically extended to higher altitudes (with 75 % integrated column located below ∼1.4 km) than NO2 , SO2 and HONO did (with 75 % integrated column below ∼0.5 km) under polluted conditions. Lifted layers were systematically observed for all species (except HONO), indicating accumulation, secondary formation or long-range transport of the pollutants at higher altitudes. Maximum values routinely occurred in the morning for NO2 , SO2 and HONO but occurred at around noon for aerosols, HCHO and CHOCHO, mainly dominated by photochemistry, characteristic upslope–downslope circulation and planetary boundary layer (PBL) dynamics. Significant day-to-day variations are found for all species due to the effect of regional transport and changes in synoptic pattern analysed with the backward propagation approach based on HYSPLIT trajectories. Low pollution was often observed for air masses from the north-west (behind cold fronts), and high pollution was observed from the southern areas such as industrialized Wu'an. The contribution of regional transport for the pollutants measured at the site during the observation period was estimated to be about 20 % to 30 % for trace gases and about 50 % for aerosols. In addition, agricultural burning events impacted the day-to-day variations in HCHO, CHOCHO and aerosols. It needs to be noted that although several MAX-DOAS measurements of trace gases and aerosols in the NCP area have been reported in previous studies, this study is the first work to derive a comprehensive set of vertical profiles of NO2 , SO2 , HONO, HCHO, CHOCHO and aerosols from measurements of one MAX-DOAS instrument. Also, so far, the validation of MAX-DOAS profile results by comparison with various surface in situ measurements as well as profile measurements from lidar and aircraft is scarce. Moreover, the backward propagation approach for characterizing the contributions of regional transport of pollutants from different regions was applied to the MAX-DOAS results of trace gases and aerosols for the first time.

The Airborne ROmanian Measurements of Aerosols and Trace gases (AROMAT) campaigns took place in Romania in September 2014 and August 2015. They focused on two sites: the Bucharest urban area and large power plants in the Jiu Valley. The main objectives of the campaigns were to test recently developed airborne observation systems dedicated to air quality studies and to verify their applicability for the validation of space-borne atmospheric missions such as the TROPOspheric Monitoring Instrument (TROPOMI)/Sentinel-5 Precursor (S5P). We present the AROMAT campaigns from the perspective of findings related to the validation of tropospheric NO2, SO2, and H2CO. We also quantify the emissions of NOx and SO2 at both measurement sites. We show that tropospheric NO2 vertical column density (VCD) measurements using airborne mapping instruments are well suited for satellite validation in principle. The signal-to-noise ratio of the airborne NO2 measurements is an order of magnitude higher than its space-borne counterpart when the airborne measurements are averaged at the TROPOMI pixel scale. However, we show that the temporal variation of the NO2 VCDs during a flight might be a significant source of comparison error. Considering the random error of the TROPOMI tropospheric NO2 VCD (σ), the dynamic range of the NO2 VCDs field extends from detection limit up to 37 σ (2.6×1016 molec. cm−2) and 29 σ (2×1016 molec. cm−2) for Bucharest and the Jiu Valley, respectively. For both areas, we simulate validation exercises applied to the TROPOMI tropospheric NO2 product. These simulations indicate that a comparison error budget closely matching the TROPOMI optimal target accuracy of 25 % can be obtained by adding NO2 and aerosol profile information to the airborne mapping observations, which constrains the investigated accuracy to within 28 %. In addition to NO2, our study also addresses the measurements of SO2 emissions from power plants in the Jiu Valley and an urban hotspot of H2CO in the centre of Bucharest. For these two species, we conclude that the best validation strategy would consist of deploying ground-based measurement systems at well-identified locations.

The Airborne ROmanian Measurements of Aerosols and Trace gases (AROMAT) campaigns took place in Romania in September 2014 and August 2015. They focused on two sites: the Bucharest urban area and the power plants in the Jiu Valley. Their main objectives were to test recently developed airborne observation systems dedicated to air quality studies and to verify the concept of such campaigns in support of the validation of spaceborne atmospheric missions such as TROPOspheric Monitoring Instrument (TROPOMI)/Sentinel-5 Precursor (S5P). We show that tropospheric NO2 vertical column density (VCD) measurements using airborne mapping instruments are valuable for satellite validation. The signal to noise ratio of the airborne NO2 measurements is one order of magnitude higher than its spaceborne counterpart when the airborne measurements are averaged at the TROPOMI pixel scale. A significant source of comparison error appears to be the time variation of the NO2 VCDs during a flight, which we estimated at about 4 x 1015 molec cm-2 in the AROMAT conditions. Considering the random error of the TROPOMI tropospheric NO2 VCD (σ), the dynamic range of the NO2 VCDs field extends from detection limit up to 37σ (2.6 x 1016 molec cm-2) or 29σ (2 x 1016 molec cm-2) for Bucharest and the Jiu Valley, respectively. For the two areas, we simulate validation exercises of the TROPOMI tropospheric NO2 product using airborne measurements. These simulations indicate that we can closely approach the TROPOMI optimal target accuracy of 25 % by adding NO2 and aerosol profile information to the mapping data, which constrains the investigated accuracy within 28 %. In addition to NO2, we also measured significant amounts of SO2 in the Jiu Valley, as well as a hotspot of H2CO in the center of Bucharest. For these two species, we conclude that the best validation strategy would consist in deploying ground-based measurement systems at key locations which the AROMAT observations help identify.

Air mass factor (AMF) calculation is the largest source of uncertainty in NO2 and HCHO satellite retrievals in situations with enhanced trace gas concentrations in the lower troposphere. Structural uncertainty arises when different retrieval methodologies are applied within the scientific community to the same satellite observations. Here, we address the issue of AMF structural uncertainty via a detailed comparison of AMF calculation methods that are structurally different between seven retrieval groups for measurements from the Ozone Monitoring Instrument (OMI). We estimate the escalation of structural uncertainty in every sub-step of the AMF calculation process. This goes beyond the algorithm uncertainty estimates provided in state-of-the-art retrievals, which address the theoretical propagation of uncertainties for one particular retrieval algorithm only. We find that top-of-atmosphere reflectances simulated by four radiative transfer models (RTMs) (DAK, McArtim, SCIATRAN and VLIDORT) agree within 1.5 %. We find that different retrieval groups agree well in the calculations of altitude resolved AMFs from different RTMs (to within 3 %), and in the tropospheric AMFs (to within 6 %) as long as identical ancillary data (surface albedo, terrain height, cloud parameters and trace gas profile) and cloud and aerosol correction procedures are being used. Structural uncertainty increases sharply when retrieval groups use their preference for ancillary data, cloud and aerosol correction. On average, we estimate the AMF structural uncertainty to be 42 % over polluted regions and 31 % over unpolluted regions, mostly driven by substantial differences in the a priori trace gas profiles, surface albedo and cloud parameters. Sensitivity studies for one particular algorithm indicate that different cloud correction approaches result in substantial AMF differences in polluted conditions (5 to 40 % depending on cloud fraction and cloud pressure, and 11 % on average) even for low cloud fractions (

In this study the consistency between MAX-DOAS measurements and radiative transfer simulations of the atmospheric O 4 absorption is investigated on two mainly clear days during the MAD-CAT campaign in Mainz, Germany, in Summer 2013. In recent years several studies indicated that measurements and radiative transfer simulations of the atmospheric O 4 absorption can only be brought into agreement if a so-called scaling factor ( 4 absorption. However, many studies, in particular based on direct sun light measurements, came to the opposite conclusion, that there is no need for a scaling factor. Up to now, there is no explanation for the observed discrepancies between measurements and simulations. Previous studies infered the need for a scaling factor from the comparison of the aerosol optical depth derived from MAX-DOAS O 4 measurements with that derived from coincident sun photometer measurements. In this study a different approach is chosen: the measured O 4 absorption at 360 nm is directly compared to the O 4 absorption obtained from radiative transfer simulations. The atmospheric conditions used as input for the radiative transfer simulations were taken from independent data sets, in particular from sun photometer and ceilometer measurements at the measurement site. The comparisons are performed for two selected clear days with similar aerosol optical depth but very different aerosol properties. For both days not only the O 4 absorptions are compared, but also all relevant error sources of the spectral analysis, the radiative transfer simulations as well as the extraction of the input parameters used for the radiative transfer simulations are quantified. One important result obtained from the analysis of synthetic spectra is that the O 4 absorptions derived from the spectral analysis agree within 1 % with the corresponding radiative transfer simulations. The performed tests and sensitivity studies might be useful for the analysis and interpretation of O 4 MAX-DOAS measurements in future studies. Different comparison results are found for both days: On 18 June, measurements and simulations agree within their (rather large) errors (the ratio of simulated and measured O 4 absorptions is found to be 1.01 ± 0.16). In contrast, on 8 July measurements and simulations significantly disagree: For the middle period of that day the ratio of simulated and measured O 4 absorptions is found to be 0.71 ± 0.12, which differs significantly from unity. Thus for that day a scaling factor is needed to bring measurements and simulations into agreement. One possible reason for the comparison results on 18 June is the rather large aerosol extinction (and its large uncertainty) close to the surface, which has a large effect on the radiative transfer simulations. Besides the inconsistent comparison results for both days, also no explanation for a O 4 scaling factor could be derived in this study. Thus similar, but more extended future studies should be performed, which preferably include more measurement days, more instruments and should be supported by more detailed independent aerosol measurements. Also additional wavelengths should be included. The MAX-DOAS measurements collected during the recent CINDI-2 campaign are probably well suited for that purpose.