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In the framework of the Europlanet 2024 Research Infrastructure Transnational Access programme, a terrestrial field campaign was conducted from 29 September to 6 October 2021 in Makgadikgadi Salt Pans (Botswana). The main goal of the campaign was to study in situ the impact of the dust devils (DDs) on the observations made by the radiometer Radiation and Dust Sensor (RDS), which is part of the Mars Environmental Dynamics Analyzer instrument, on board NASA’s Mars 2020 Perseverance rover. Several DDs and dust lifting events caused by non-vortex wind gusts were detected using the RDS, and the different impacts of these events were analyzed in the observations. DD diameter, advection velocity, and trajectory were derived from the RDS observations, and then, panoramic videos of such events were used to validate these results. The instrument signal variations produced by dust lifting (by vortices or wind gusts) in Makgadikgadi Pans are similar to those observed on Mars with the RDS, showing the potential of this location as a Martian DD analog.

This paper reports on ground-based validation of the atmospheric OClO data record produced within the framework of EUMETSAT's Satellite Application Facility on Atmospheric Chemistry Monitoring (AC SAF) using the Global Ozone Monitoring Experiment (GOME)-2A and GOME-2B instrument measurements, covering the 2007–2016 and 2013–2016 periods, respectively. OClO slant column densities are compared to correlative measurements collected from nine Zenith-Scattered-Light Differential Optical Absorption Spectroscopy (ZSL-DOAS) instruments from the Network for the Detection of Atmospheric Composition Change (NDACC) distributed in both the Arctic and Antarctic. Sensitivity tests are performed on the ground-based data to estimate the impact of the different OClO DOAS analysis settings. On this basis, we infer systematic uncertainties of about 25 % (i.e., about 3.75×1013 molec. cm−2) between the different ground-based data analyses, reaching total uncertainties ranging from about 26 % to 33 % for the different stations (i.e., around 4 to 5×1013 molec. cm−2). Time series at the different sites show good agreement between satellite and ground-based data for both the inter-annual variability and the overall OClO seasonal behavior. GOME-2A results are found to be noisier than those of GOME-2B, especially after 2011, probably due to instrumental degradation effects. Daily linear regression analysis for OClO-activated periods yield correlation coefficients of 0.8 for GOME-2A and 0.87 for GOME-2B, with slopes with respect to the ground-based data ensemble of 0.64 and 0.72, respectively. Satellite minus ground-based offsets are within 8×1013 molec. cm−2, with some differences between GOME-2A and GOME-2B depending on the station. Overall, considering all the stations, a median offset of about -2.2×1013 molec. cm−2 is found for both GOME-2 instruments.

Every year, large-scale African dust outbreaks frequently pass over the Canary Islands (Spain). Here we describe the seasonal evolution of atmospheric aerosol extinction and meteorological vertical profiles on Tenerife over the period 2007–2018 using long-term micropulse lidar (MPL-3) and radiosonde observations. These measurements are used to categorise the different patterns of dust transport over the subtropical North Atlantic and, for the first time, to robustly describe the dust vertical distribution in the Saharan Air Layer (SAL) over this region. Three atmospheric scenarios dominate the aerosol climatology: dust-free (clean) conditions, the Saharan summer scenario (summer-SAL) and the Saharan winter scenario (winter-SAL). A relatively well-mixed marine boundary layer (MBL) was observed in the case of clean (dust-free) conditions; it was associated with rather constant lidar extinction coefficients (α) below 0.036 km−1 with minimum α (< 0.022 km−1) in the free troposphere (FT). The summer-SAL has been characterised as a dust-laden layer strongly affecting both the MBL (Δα = +48 % relative to clean conditions) and the FT. The summer-SAL appears as a well-stratified layer, relatively dry at lower levels (Δr∼-44 % at the SAL’s base, where r is the water vapour mixing ratio) but more humid at higher levels compared with clean FT conditions (Δr∼+332 % at 5.3 km), with a peak of α> 0.066 km−1 at ∼ 2.5 km. Desert dust is present up to ∼ 6.0 km, the SAL top based on the altitude of SAL's temperature inversion. In the winter-SAL scenario, the dust layer is confined to lower levels below 2 km altitude. This layer is characterised by a dry anomaly at lower levels (Δr∼ −38 % in comparison to the clean scenario) and a dust peak at ∼ 1.3 km height. Clean FT conditions were found above 2.3 km. Our results reveal the important role that both dust and water vapour play in the radiative balance within the summer-SAL and winter-SAL. The dominant dust-induced shortwave (SW) radiative warming in summer (heating rates up to +0.7 K d−1) is found slightly below the dust maximum. However, the dominant contribution of water vapour was observed as a net SW warming observed within the SAL (from 2.1 to 5.7 km) and as a strong cold anomaly near the SAL's top (−0.6 K d−1). The higher water vapour content found to be carried on the summer-SAL, despite being very low, represents a high relative variation in comparison to the very dry clean free troposphere in the subtropics. This relevant aspect should be properly taken into account in atmospheric modelling processes. In the case of the winter-SAL, we observed a dust-induced radiative effect dominated by SW heating (maximum heating of +0.7 K d−1 at 1.5 km, near the dust peak); both dust and atmospheric water vapour impact heating in the atmospheric column. This is the case of the SW heating within the SAL (maximum near the r peak), the dry anomaly at lower levels (Δr∼ −38 % at 1 km) and the thermal cooling (∼ 0.3 K d−1) from the temperature inversion upwards. Finally, we hypothesise that the SAL can impact heterogeneous ice nucleation processes through the frequent occurrence of mid-level clouds observed near the SAL top at relatively warm temperatures. A dust event that affected Tenerife on August 2015 is simulated using the regional DREAM model to assess the role of dust and water vapour carried within SAL in the ice nucleation processes. The modelling results reproduce the arrival of the dust plume and its extension over the island and confirm the observed relationship between the summer-SAL conditions and the formation of mid- and high-level clouds.

Aerosol particles are a complex component of the atmospheric system which influence climate directly by interacting with solar radiation, and indirectly by contributing to cloud formation. The variety of their sources, as well as the multiple transformations they may undergo during their transport (including wet and dry deposition), result in significant spatial and temporal variability of their properties. Documenting this variability is essential to provide a proper representation of aerosols and cloud condensation nuclei (CCN) in climate models. Using measurements conducted in 2016 or 2017 at 62 ground-based stations around the world, this study provides the most up-to-date picture of the spatial distribution of particle number concentration (Ntot) and number size distribution (PNSD, from 39 sites). A sensitivity study was first performed to assess the impact of data availability on Ntot's annual and seasonal statistics, as well as on the analysis of its diel cycle. Thresholds of 50 % and 60 % were set at the seasonal and annual scale, respectively, for the study of the corresponding statistics, and a slightly higher coverage (75 %) was required to document the diel cycle. Although some observations are common to a majority of sites, the variety of environments characterizing these stations made it possible to highlight contrasting findings, which, among other factors, seem to be significantly related to the level of anthropogenic influence. The concentrations measured at polar sites are the lowest (∼ 102 cm−3) and show a clear seasonality, which is also visible in the shape of the PNSD, while diel cycles are in general less evident, due notably to the absence of a regular day–night cycle in some seasons. In contrast, the concentrations characteristic of urban environments are the highest (∼ 103–104 cm−3) and do not show pronounced seasonal variations, whereas diel cycles tend to be very regular over the year at these stations. The remaining sites, including mountain and non-urban continental and coastal stations, do not exhibit as obvious common behaviour as polar and urban sites and display, on average, intermediate Ntot (∼ 102–103 cm−3). Particle concentrations measured at mountain sites, however, are generally lower compared to nearby lowland sites, and tend to exhibit somewhat more pronounced seasonal variations as a likely result of the strong impact of the atmospheric boundary layer (ABL) influence in connection with the topography of the sites. ABL dynamics also likely contribute to the diel cycle of Ntot observed at these stations. Based on available PNSD measurements, CCN-sized particles (considered here as either >50 nm or >100 nm) can represent from a few percent to almost all of Ntot, corresponding to seasonal medians on the order of ∼ 10 to 1000 cm−3, with seasonal patterns and a hierarchy of the site types broadly similar to those observed for Ntot. Overall, this work illustrates the importance of in situ measurements, in particular for the study of aerosol physical properties, and thus strongly supports the development of a broad global network of near surface observatories to increase and homogenize the spatial coverage of the measurements, and guarantee as well data availability and quality. The results of this study also provide a valuable, freely available and easy to use support for model comparison and validation, with the ultimate goal of contributing to improvement of the representation of aerosol–cloud interactions in models, and, therefore, of the evaluation of the impact of aerosol particles on climate.

High-resolution Fourier transform infrared (FTIR) solar observations are particularly relevant for climate studies, as they allow atmospheric gaseous composition and multiple climate processes to be monitored in detail. In this context, the present paper provides an overview of 20 years of FTIR measurements taken in the framework of the NDACC (Network for the Detection of Atmospheric Composition Change) from 1999 to 2018 at the subtropical Izaña Observatory (IZO, Spain). Firstly, long-term instrumental performance is comprehensively assessed, corroborating the temporal stability and reliable instrumental characterization of the two FTIR spectrometers installed at IZO since 1999. Then, the time series of all trace gases contributing to NDACC at IZO are presented (i.e. C2H6, CH4, ClONO2, CO, HCl, HCN, H2CO, HF, HNO3, N2O, NO2, NO, O3, carbonyl sulfide (OCS), and water vapour isotopologues H216O, H218O, and HD16O), reviewing the major accomplishments drawn from these observations. In order to examine the quality and long-term consistency of the IZO FTIR observations, a comparison of those NDACC products for which other high-quality measurement techniques are available at IZO has been performed (i.e. CH4, CO, H2O, NO2, N2O, and O3). This quality assessment was carried out on different timescales to examine what temporal signals are captured by the FTIR records, and to what extent. After 20 years of operation, the IZO NDACC FTIR observations have been found to be very consistent and reliable over time, demonstrating great potential for climate research. Long-term NDACC FTIR data sets, such as IZO, are indispensable tools for the investigation of atmospheric composition trends, multi-year phenomena, and complex climate feedback processes, as well as for the validation of past and present space-based missions and chemistry climate models.

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.

This paper reports on consolidated ground-based validation results of the atmospheric NO2 data produced operationally since April 2018 by the TROPOspheric Monitoring Instrument (TROPOMI) on board of the ESA/EU Copernicus Sentinel-5 Precursor (S5P) satellite. Tropospheric, stratospheric, and total NO2 column data from S5P are compared to correlative measurements collected from, respectively, 19 Multi-Axis Differential Optical Absorption Spectroscopy (MAX-DOAS), 26 Network for the Detection of Atmospheric Composition Change (NDACC) Zenith-Scattered-Light DOAS (ZSL-DOAS), and 25 Pandonia Global Network (PGN)/Pandora instruments distributed globally. The validation methodology gives special care to minimizing mismatch errors due to imperfect spatio-temporal co-location of the satellite and correlative data, e.g. by using tailored observation operators to account for differences in smoothing and in sampling of atmospheric structures and variability and photochemical modelling to reduce diurnal cycle effects. Compared to the ground-based measurements, S5P data show, on average, (i) a negative bias for the tropospheric column data, of typically −23 % to −37 % in clean to slightly polluted conditions but reaching values as high as −51 % over highly polluted areas; (ii) a slight negative median difference for the stratospheric column data, of about −0.2 Pmolec cm−2, i.e. approx. −2 % in summer to −15 % in winter; and (iii) a bias ranging from zero to −50 % for the total column data, found to depend on the amplitude of the total NO2 column, with small to slightly positive bias values for columns below 6 Pmolec cm−2 and negative values above. The dispersion between S5P and correlative measurements contains mostly random components, which remain within mission requirements for the stratospheric column data (0.5 Pmolec cm−2) but exceed those for the tropospheric column data (0.7 Pmolec cm−2). While a part of the biases and dispersion may be due to representativeness differences such as different area averaging and measurement times, it is known that errors in the S5P tropospheric columns exist due to shortcomings in the (horizontally coarse) a priori profile representation in the TM5-MP chemical transport model used in the S5P retrieval and, to a lesser extent, to the treatment of cloud effects and aerosols. Although considerable differences (up to 2 Pmolec cm−2 and more) are observed at single ground-pixel level, the near-real-time (NRTI) and offline (OFFL) versions of the S5P NO2 operational data processor provide similar NO2 column values and validation results when globally averaged, with the NRTI values being on average 0.79 % larger than the OFFL values.

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.

Aerosol particles are essential constituents of the Earth's atmosphere, impacting the earth radiation balance directly by scattering and absorbing solar radiation, and indirectly by acting as cloud condensation nuclei. In contrast to most greenhouse gases, aerosol particles have short atmospheric residence times, resulting in a highly heterogeneous distribution in space and time. There is a clear need to document this variability at regional scale through observations involving, in particular, the in situ near-surface segment of the atmospheric observation system. This paper will provide the widest effort so far to document variability of climate-relevant in situ aerosol properties (namely wavelength dependent particle light scattering and absorption coefficients, particle number concentration and particle number size distribution) from all sites connected to the Global Atmosphere Watch network. High-quality data from almost 90 stations worldwide have been collected and controlled for quality and are reported for a reference year in 2017, providing a very extended and robust view of the variability of these variables worldwide. The range of variability observed worldwide for light scattering and absorption coefficients, single-scattering albedo, and particle number concentration are presented together with preliminary information on their long-term trends and comparison with model simulation for the different stations. The scope of the present paper is also to provide the necessary suite of information, including data provision procedures, quality control and analysis, data policy, and usage of the ground-based aerosol measurement network. It delivers to users of the World Data Centre on Aerosol, the required confidence in data products in the form of a fully characterized value chain, including uncertainty estimation and requirements for contributing to the global climate monitoring system.

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.

Particle extinction-to-backscatter ratio (lidar ratio) is a key parameter for a correct interpretation of elastic lidar measurements. Of particular importance is the determination of the lidar ratio of the Saharan Air Layer mineral dust transported into the free troposphere over the North Atlantic region. The location of the two sun photometer stations managed by the Izaña Atmospheric Research Centre (IARC) on the island of Tenerife and a decade of available micropulse lidar (MPL) data allow us to determine the lidar ratio under almost pure-dust conditions. This result can be considered representative of the Saharan dust transported westward over the North Atlantic in the subtropical belt. Three different methods have been used to calculate the lidar ratio in this work: (1) using the inversion of sky radiance measurements from a sun–sky photometer installed at the Izaña Observatory (2373 m a.s.l.) under free-troposphere conditions; (2) the one-layer method, a joint determination using a micropulse lidar sited at the Santa Cruz de Tenerife sea-level station and photometric information considering one layer of aerosol characterized by a single lidar ratio; and (3) the two-layer method, a joint determination using the micropulse lidar and photometric information considering two layers of aerosol with two different lidar ratios. The one-layer method only uses data from a co-located photometer at Santa Cruz de Tenerife, while the two-layer conceptual approach incorporates photometric information at two heights from the observatories of Izaña and Santa Cruz de Tenerife. The almost pure-dust lidar ratio retrieval from the sun–sky photometer and from the two-layer method give similar results, with lidar ratios at 523 nm of 49 ± 6 and 50 ± 11 sr. These values obtained from a decade of data records are coincident with other studies in the literature reporting campaigns in the subtropical North Atlantic region. This result shows that the two-layer method is an improved conceptual approach compared to the single-layer approach, which matches the real lower-troposphere structure well. The two-layer method is able to retrieve reliable lidar ratios and therefore aerosol extinction profiles despite the inherent limitations of the elastic lidar technique. We found a lack of correlation between lidar ratio and Ångström exponent (α), which indicates that the dust lidar ratio can be considered independent of dust size distribution in this region. This finding suggests that dust is, under most atmospheric conditions, the predominant aerosol in the North Atlantic free troposphere, which is in agreement with previous studies conducted at the Izaña Observatory.

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 () is applied to the measured O4 absorption. However, many studies, including those based on direct sunlight measurements, came to the opposite conclusion, that there is no need for a scaling factor. Up to now, there is no broad consensus for an explanation of the observed discrepancies between measurements and simulations. Previous studies inferred the need for a scaling factor from the comparison of the aerosol optical depths derived from MAX-DOAS O4 measurements with that derived from coincident sun photometer measurements. In this study a different approach is chosen: the measured O4 absorption at 360 nm is directly compared to the O4 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. This study has three main goals: first all relevant error sources of the spectral analysis, the radiative transfer simulations and 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 O4 absorptions derived from the spectral analysis agree within 1 % with the corresponding radiative transfer simulations at 360 nm. Based on the results from sensitivity studies, recommendations for optimised settings for the spectral analysis and radiative transfer simulations are given. Second, the measured and simulated results are compared for 2 selected cloud-free days with similar aerosol optical depths but very different aerosol properties. On 18 June, measurements and simulations agree within their (rather large) uncertainties (the ratio of simulated and measured O4 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 O4 absorptions is found to be 0.82±0.10, which differs significantly from unity. Thus, for that day a scaling factor is needed to bring measurements and simulations into agreement. Third, recommendations for further intercomparison exercises are derived. One important recommendation for future studies is that aerosol profile data should be measured at the same wavelengths as the MAX-DOAS measurements. Also, the altitude range without profile information close to the ground should be minimised and detailed information on the aerosol optical and/or microphysical properties should be collected and used. The results for both days are inconsistent, and no explanation for a O4 scaling factor could be derived in this study. Thus, similar but more extended future studies should be performed, including more measurement days and more instruments. Also, additional wavelengths should be included.

For decades, reactive halogen species (RHSs) have been the subject of detailed scientific research due to their influence on the oxidizing capacity of the atmosphere and on the climate. From the RHSs, those containing bromine are of particular interest in the polar troposphere as a result of their link to ozone-depletion events (ODEs) and to the perturbation of the cycle of toxic mercury, for example. Given its remoteness and related limited accessibility compared to the Arctic region, the RHSs in the Antarctic troposphere are still poorly characterized. This work presents ground-based observations of tropospheric BrO from two different Antarctic locations: Marambio Base (64°13′ S, 56°37′ W) and Belgrano II Base (77°52′ S, 34°7′ W) during the sunlit period of 2015. By means of MAX-DOAS (Multi-axis Differential Optical Absorption Spectroscopy) measurements of BrO performed from the two research sites, the seasonal variation in this reactive trace gas is described along with its vertical and geographical distribution in the Antarctic environment. Results show an overall vertical profile of BrO mixing ratio decreasing with altitude, with a median value of 1.6 pmol mol−1 in the lowest layers of the troposphere. Additionally, observations show that the polar sunrise triggers a geographical heterogeneous increase in bromine content in the Antarctic troposphere yielding a maximum BrO at Marambio (26 pmol mol−1), amounting to 3-fold the values observed at Belgrano at dawn. Data presented herein are combined with previous studies and ancillary data to update and expand our knowledge of the geographical and vertical distribution of BrO in the Antarctic troposphere, revealing Marambio as one of the locations with the highest BrO reported so far in Antarctica. Furthermore, the observations gathered during 2015 serve as a proxy to investigate the budget of reactive bromine (BrOx = Br + BrO) and the bromine-mediated ozone loss rate in the Antarctic troposphere.

Over 20 years of stratospheric NO2 vertical column density (VCD) data from ground-based zenith DOAS spectrometers were used for trend analysis, specifically, via multiple linear regression. Spectrometers from the Network for the Detection of Atmospheric Composition Change (NDACC) cover the subtropical latitudes in the Northern Hemisphere (Izaña, 28° N), the southern Subantarctic (Ushuaia, 55° S) and Antarctica (Marambio, 64° S, and Belgrano, 78° S). The results show that for the period 1993–2014, a mean positive decadal trend of +8.7 % was found in the subtropical Northern Hemisphere stations, and negative decadal trends of −8.7 and −13.8 % were found in the Southern Hemisphere at Ushuaia and Marambio, respectively; all trends are statistically significant at 95 %. Belgrano only shows a significant decadal trend of −11.3 % in the summer/autumn period. Most of the trends result from variations after 2005. The trend in the diurnal build-up per hour (DBU) was used to estimate the change in the rate of N2O5 conversion to NO2 during the day. With minor differences, the results reproduce those obtained for NO2. The trends computed for individual months show large month-to-month variability. At Izaña, the maximum occurs in December (+13.1 %), dropping abruptly to lower values in the first part of the year. In the Southern Hemisphere, the polar vortex dominates the monthly distributions of the trends. At Marambio, the maximum occurs in mid-winter (−21 %), whereas at the same time, the Ushuaia trend is close to its annual minimum (−7 %). The large difference in the trends at these two relatively close stations suggests a vortex shift towards the Atlantic/South American area over the past few years. Finally, the hemispheric asymmetry obtained in this work is discussed in the framework of the results obtained by previous works that considered tracer analysis and Brewer–Dobson circulation. The results obtained here provide evidence that the NO2 produced by N2O decomposition is not the only cause of the observed trend in the stratosphere and support recent publications pointing to a dynamical redistribution starting in the past decade.

This work is a first approach to correct the systematic errors observed in the aerosol optical depth (AOD) retrieved at nighttime using lunar photometry and calibration techniques dependent on the lunar irradiance model. To this end, nocturnal AOD measurements were performed in 2014 using the CE318-T master Sun–sky–lunar photometer (lunar Langley calibrated) at the Izaña high mountain observatory. This information has been restricted to 59 nights characterized as clean and stable according to lidar vertical profiles. A phase angle dependence as well as an asymmetry within the Moon's cycle of the Robotic Lunar Observatory (ROLO) model could be deduced from the comparison in this 59-night period of the CE318-T calibration performed by means of the lunar Langley calibration and the calibration performed every single night by means of the common Langley technique. Nocturnal AOD has also been compared in the same period with a reference AOD based on daylight AOD extracted from the AErosol RObotic NETwork (AERONET) at the same station. Considering stable conditions, the difference ΔAODfit, between AOD from lunar observations and the linearly interpolated AOD (the reference) from daylight data, has been calculated. The results show that ΔAODfit values are strongly affected by the Moon phase and zenith angles. This dependency has been parameterized using an empirical model with two independent variables (Moon phase and zenith angles) in order to correct the AOD for these residual dependencies. The correction of this parameterized dependency has been checked at four stations with quite different environmental conditions (Izaña, Lille, Carpentras and Dakar) showing a significant reduction of the AOD dependence on phase and zenith angles and an improved agreement with daylight reference data. After the correction, absolute AOD differences for day–night–day clean and stable transitions remain below 0.01 for all wavelengths.

We validate the Ozone Monitoring Instrument (OMI) Ozone Profile (PROFOZ) product from October 2004 through December 2014 retrieved by the Smithsonian Astrophysical Observatory (SAO) algorithm against ozonesonde observations. We also evaluate the effects of OMI row anomaly (RA) on the retrieval by dividing the dataset into before and after the occurrence of serious OMI RA, i.e., pre-RA (2004–2008) and post-RA (2009–2014). The retrieval shows good agreement with ozonesondes in the tropics and midlatitudes and for pressure ∼ 50 hPa after applying OMI averaging kernels to ozonesonde data. The MBs of the stratospheric ozone column (SOC, the ozone column from the tropopause pressure to the ozonesonde burst pressure) are within 2 % with SDs of ∼ 50 hPa. The SOC MBs increase up to 3 % with SDs as great as 6 % and the TOC SDs increase up to 30 %. The comparison generally degrades at larger solar zenith angles (SZA) due to weaker signals and additional sources of error, leading to worse performance at high latitudes and during the midlatitude winter. Agreement also degrades with increasing cloudiness for pressure > ∼ 100 hPa and varies with cross-track position, especially with large MBs and SDs at extreme off-nadir positions. In the tropics and midlatitudes, the post-RA comparison is considerably worse with larger SDs reaching 2 % in the stratosphere and 8 % in the troposphere and up to 6 % in TOC. There are systematic differences that vary with latitude compared to the pre-RA comparison. The retrieval comparison demonstrates good long-term stability during the pre-RA period but exhibits a statistically significant trend of 0.14–0.7 % year−1 for pressure −1 in SOC, and −0. 33 DU year−1 in TOC during the post-RA period. The spatiotemporal variation of retrieval performance suggests the need to improve OMI's radiometric calibration especially during the post-RA period to maintain the long-term stability and reduce the latitude/season/SZA and cross-track dependency of retrieval quality.

The differential optical absorption spectroscopy (DOAS) method is a well-known remote sensing technique that is nowadays widely used for measurements of atmospheric trace gases, creating the need for harmonization and characterization efforts. In this study, an intercomparison exercise of DOAS retrieval codes from 17 international groups is presented, focusing on NO2 slant columns. The study is based on data collected by one instrument during the Multi-Axis DOAS Comparison campaign for Aerosols and Trace gases (MAD-CAT) in Mainz, Germany, in summer 2013. As data from the same instrument are used by all groups, the results are free of biases due to instrumental differences, which is in contrast to previous intercomparison exercises.While in general an excellent correlation of NO2 slant columns between groups of > 99.98 % (noon reference fits) and > 99.2 % (sequential reference fits) for all elevation angles is found, differences between individual retrievals are as large as 8 % for NO2 slant columns and 100 % for rms residuals in small elevation angles above the horizon.Comprehensive sensitivity studies revealed that absolute slant column differences result predominantly from the choice of the reference spectrum while relative differences originate from the numerical approach for solving the DOAS equation as well as the treatment of the slit function. Furthermore, differences in the implementation of the intensity offset correction were found to produce disagreements for measurements close to sunrise (8–10 % for NO2, 80 % for rms residual). The largest effect of ≈ 8 % difference in NO2 was found to arise from the reference treatment; in particular for fits using a sequential reference. In terms of rms fit residual, the reference treatment has only a minor impact. In contrast, the wavelength calibration as well as the intensity offset correction were found to have the largest impact (up to 80 %) on rms residual while having only a minor impact on retrieved NO2 slant columns.

This paper presents the new photometer CE318-T, able to perform daytime and night-time photometric measurements using the sun and the moon as light source. Therefore, this new device permits a complete cycle of diurnal aerosol and water vapour measurements valuable to enhance atmospheric monitoring to be extracted. In this study we have found significantly higher precision of triplets when comparing the CE318-T master instrument and the Cimel AErosol RObotic NETwork (AERONET) master (CE318-AERONET) triplets as a result of the new CE318-T tracking system. Regarding the instrument calibration, two new methodologies to transfer the calibration from a reference instrument using only daytime measurements (Sun Ratio and Sun-Moon gain factor techniques) are presented and discussed. These methods allow the reduction of the previous complexities inherent to nocturnal calibration. A quantitative estimation of CE318-T AOD uncertainty by means of error propagation theory during daytime revealed AOD uncertainties (uDAOD) for Langley-calibrated instruments similar to the expected values for other reference instruments (0.002–0.009). We have also found uDAOD values similar to the values reported in sun photometry for field instruments ( ∼ 0.015). In the case of the night-time period, the CE318-T-estimated standard combined uncertainty (uNAOD) is dependent not only on the calibration technique but also on illumination conditions and the instrumental noise. These values range from 0.011–0.018 for Lunar Langley-calibrated instruments to 0.012–0.021 for instruments calibrated using the Sun Ratio technique. In the case of moon-calibrated instruments using the Sun-Moon gain factor method and sun-calibrated using the Langley technique, we found uNAOD ranging from 0.016 to 0.017 (up to 0.019 in 440 nm channel), not dependent on any lunar irradiance model.A subsequent performance evaluation including CE318-T and collocated measurements from independent reference instruments has served to assess the CE318-T performance as well as to confirm its estimated uncertainty. Daytime AOD evaluation, performed at Izaña station from March to June 2014, encompassed measurements from a reference CE318-T, a CE318-AERONET master instrument, a Precision Filter Radiometer (PFR) and a Precision Spectroradiometer (PSR) prototype, reporting low AOD discrepancies between the four instruments (up to 0.006). The nocturnal AOD evaluation was performed using CE318-T- and star-photometer-collocated measurements and also by means of a day/night coherence transition test using the CE318-T master instrument and the CE318 daytime data from the CE318-AERONET master instrument. Results showed low discrepancies with the star photometer at 870 and 500 nm channels ( ≤ 0.013) and differences with AERONET daytime data (1 h after and before sunset and sunrise) in agreement with the estimated uNAOD values at all illumination conditions in the case of channels within the visible spectral range, and only for high moon's illumination conditions in the case of near-infrared channels.Precipitable water vapour (PWV) validation showed a good agreement between CE318-T and Global Navigation Satellite System (GNSS) PWV values for all illumination conditions, within the expected precision for sun photometry.Finally, two case studies have been included to highlight the ability of the new CE318-T to capture the diurnal cycle of aerosols and water vapour as well as short-term atmospheric variations, critical for climate studies.

Thirteen years of ozone soundings at the Antarctic Belgrano II station (78° S, 34.6° W) have been analysed to establish a climatology of stratospheric ozone and temperature over the area. The station is inside the polar vortex during the period of development of chemical ozone depletion. Weekly periodic profiles provide a suitable database for seasonal characterization of the evolution of stratospheric ozone, especially valuable during wintertime, when satellites and ground-based instruments based on solar radiation are not available. The work is focused on ozone loss rate variability (August–October) and its recovery (November–December) at different layers identified according to the severity of ozone loss. The time window selected for the calculations covers the phase of a quasi-linear ozone reduction, around day 220 (mid-August) to day 273 (end of September). Decrease of the total ozone column over Belgrano during spring is highly dependent on the meteorological conditions. Largest depletions (up to 59%) are reached in coldest years, while warm winters exhibit significantly lower ozone loss (20%). It has been found that about 11% of the total O3 loss, in the layer where maximum depletion occurs, takes place before sunlight has arrived, as a result of transport to Belgrano of air from a somewhat lower latitude, near the edge of the polar vortex, providing evidence of mixing inside the vortex. Spatial homogeneity of the vortex has been examined by comparing Belgrano results with those previously obtained for South Pole station (SPS) for the same altitude range and for 9 yr of overlapping data. Results show more than 25% higher ozone loss rate at SPS than at Belgrano. The behaviour can be explained taking into account (i) the transport to both stations of air from a somewhat lower latitude, near the edge of the polar vortex, where sunlight reappears sooner, resulting in earlier depletion of ozone, and (ii) the accumulated hours of sunlight, which become much greater at the South Pole after the spring equinox. According to the variability of the ozone hole recovery, a clear connection between the timing of the breakup of the vortex and the monthly ozone content was found. Minimum ozone concentration of 57 DU in the 12–24 km layer remained in November, when the vortex is more persistent, while in years when the final stratospheric warming took place "very early", mean integrated ozone rose by up to 160–180 DU.

Polar stratospheric clouds (PSCs) play an important role in polar ozone depletion, since they are involved in diverse ozone destruction processes (chlorine activation, denitrification). The degree of that ozone reduction is depending on the type of PSCs, and hence on their occurrence. Therefore PSC characterization, mainly focused on PSC-type discrimination, is widely demanded. The backscattering (R) and volume linear depolarization (δV) ratios are the parameters usually used in lidar measurements for PSC detection and identification. In this work, an improved version of the standard NASA/Micro Pulse Lidar (MPL-4), which includes a built-in depolarization detection module, has been used for PSC observations above the coastal Antarctic Belgrano II station (Argentina, 77.9° S 34.6° W, 256 m a.s.l.) since 2009. Examination of the MPL-4 δV feature as a suitable index for PSC-type discrimination is based on the analysis of the two-channel data, i.e., the parallel (p-) and perpendicular (s-) polarized MPL signals. This study focuses on the comparison of coincident δV-profiles as obtained from ground-based MPL-4 measurements during three Antarctic winters with those reported from the space-borne lidar CALIOP (Cloud-Aerosol Lidar with Orthogonal Polarization) aboard the CALIPSO (Cloud-Aerosol Lidar and Infrared Pathfinder Satellite Observation) satellite in the same period (83 simultaneous cases are analysed for 2009–2011 austral winter times). Three different approaches are considered for the comparison analysis between both lidar profile data sets in order to test the degree of agreement: the correlation coefficient (CC), as a measure of the relationship between both PSC vertical structures; the mean differences together with their root mean square (RMS) values found between data sets; and the percentage differences (BIAS), parameter also used in profiling comparisons between CALIOP and other ground-based lidar systems. All of them are examined as a function of the CALIPSO ground-track distance from the Belgrano II station. Results represent a relatively good agreement between both ground-based MPL-4 and space-borne CALIOP profiles of the volume linear depolarization ratio δV for PSC events, once the MPL-4 depolarization calibration parameters are applied. Discrepancies between CALIOP and MPL-4 profiles in vertical layering structure are enhanced from 20 km up, likely due to a decrease of the signal-to-noise ratio (SNR) for both lidar systems at those altitudes. Regarding the results obtained from the mean and the percentage differences found between MPL-4 and CALIOP δV profiles, a predominance of negative values is also observed, indicating a generalized underestimation of the MPL-4 depolarization as compared to that reported by CALIOP. However, absolute differences between those δV-profile data sets are no higher than a 10 ± 11% in average. Moreover, the degree of agreement between both lidar δV data sets is slightly dependent on the CALIPSO ground-track overpass distance from the Belgrano II station. That is, small discrepancies are found when CALIPSO ground-track distance is as close as far from the ground-based station. These results would indicate that MPL-4 depolarization observations would reflect relatively well the PSC field that CALIOP can detect at relatively large distances from the ground-based station. As a consequence, PSC properties can be statistically similar, on average, over large volumes, and hence the present weak disagreement found between both the lidar δV data sets can be likely dominated by small spatial PSC inhomogeneities along the CALIPSO separation from the station. This statement is based on the fact that Belgrano II is a station located well inside the stable Antarctic polar vortex, allowing determined thermodynamic conditions leading to a very low variability in the PSC field, and in their properties.

To probe the spatial extent of tropospheric ozone depletion events during Antarctic spring, a network of 10 autonomous ozone monitors was established around the Dronning Maud Land sector of Antarctica for a full calendar year. Together with manned stations in the area, the network covered a ~1200 km stretch of coast, as well as a transect ~300 km inland and to ~2000 m above sea level (a.s.l.). Here we present results from the spring period (August to October 2008). While some ozone depletion events were evident at only a single site, implying localised ozone destruction, others were evident across the network. The fact that, on occasions, ozone depletion events were observed at all coastal sites simultaneously, suggests the depleted air mass had a scale of at least 1200 km. As the ozone-poor air was advected from the Weddell Sea sea ice zone, the data imply that large areas over the Weddell Sea sea ice zone are significantly depleted in ozone on occasions during Antarctic spring.

From June to July 2009 more than thirty different in-situ and remote sensing instruments from all over the world participated in the Cabauw Intercomparison campaign for Nitrogen Dioxide measuring Instruments (CINDI). The campaign took place at KNMI's Cabauw Experimental Site for Atmospheric Research (CESAR) in the Netherlands. Its main objectives were to determine the accuracy of state-of-the-art ground-based measurement techniques for the detection of atmospheric nitrogen dioxide (both in-situ and remote sensing), and to investigate their usability in satellite data validation. The expected outcomes are recommendations regarding the operation and calibration of such instruments, retrieval settings, and observation strategies for the use in ground-based networks for air quality monitoring and satellite data validation. Twenty-four optical spectrometers participated in the campaign, of which twenty-one had the capability to scan different elevation angles consecutively, the so-called Multi-axis DOAS systems, thereby collecting vertical profile information, in particular for nitrogen dioxide and aerosol. Various in-situ samplers and lidar instruments simultaneously characterized the variability of atmospheric trace gases and the physical properties of aerosol particles. A large data set of continuous measurements of these atmospheric constituents has been collected under various meteorological conditions and air pollution levels. Together with the permanent measurement capability at the CESAR site characterizing the meteorological state of the atmosphere, the CINDI campaign provided a comprehensive observational data set of atmospheric constituents in a highly polluted region of the world during summertime. First detailed comparisons performed with the CINDI data show that slant column measurements of NO2, O4 and HCHO with MAX-DOAS agree within 5 to 15%, vertical profiles of NO2 derived from several independent instruments agree within 25% of one another, and MAX-DOAS aerosol optical thickness agrees within 20–30% with AERONET data. For the in-situ NO2 instrument using a molybdenum converter, a bias was found as large as 5 ppbv during day time, when compared to the other in-situ instruments using photolytic converters.

In June 2009, 22 spectrometers from 14 institutes measured tropospheric and stratospheric NO2 from the ground for more than 11 days during the Cabauw Intercomparison Campaign of Nitrogen Dioxide measuring Instruments (CINDI), at Cabauw, NL (51.97° N, 4.93° E). All visible instruments used a common wavelength range and set of cross sections for the spectral analysis. Most of the instruments were of the multi-axis design with analysis by differential spectroscopy software (MAX-DOAS), whose non-zenith slant columns were compared by examining slopes of their least-squares straight line fits to mean values of a selection of instruments, after taking 30-min averages. Zenith slant columns near twilight were compared by fits to interpolated values of a reference instrument, then normalised by the mean of the slopes of the best instruments. For visible MAX-DOAS instruments, the means of the fitted slopes for NO2 and O4 of all except one instrument were within 10% of unity at almost all non-zenith elevations, and most were within 5%. Values for UV MAX-DOAS instruments were almost as good, being 12% and 7%, respectively. For visible instruments at zenith near twilight, the means of the fitted slopes of all instruments were within 5% of unity. This level of agreement is as good as that of previous intercomparisons, despite the site not being ideal for zenith twilight measurements. It bodes well for the future of measurements of tropospheric NO2, as previous intercomparisons were only for zenith instruments focussing on stratospheric NO2, with their longer heritage.

Daily NO2 vertical column density (VCD) has been routinely measured by zenith sky spectroscopy at the subtropical station of Izaña (28° N, 16° W) since 1993 in the framework of the Network for the Detection of Atmospheric Composition Change (NDACC). Based on 14 years of data the first low latitude NO2 VCD climatology has been established and the main characteristics from short timescales of one day to interannual variability are presented. Instrumental descriptions and different sources of errors are described in detail. The observed diurnal cycle follows that expected by gas-phase NOx chemistry, as can be shown by the good agreement with a vertically integrated chemical box model, and is modulated by solar radiation. The seasonal evolution departs from the phase of the hours of daylight, indicating the signature of upper stratospheric temperature changes. From the data record (1993–2006) no significant long-term trends in NO2 VCD can be inferred. Comparison of the ground-based data sets with nadir-viewing satellite spectrometers shows excellent agreement for SCIAMACHY with differences between both datasets of 1.1%. GOME displays unrealistic features with the largest discrepancies during summer. The ground-based data are compared with long-term output of the SLIMCAT 3-D chemical transport model (CTM). The basic model, forced by ECMWF (ERA-40) analyses, captures the observed NO2 annual cycle but significantly underestimates the spring/summer maximum (by 12% at sunset and up to 25% at sunrise). In a model run which uses assimilation of satellite CH4 profiles to constrain the model long-lived tracers the agreement is significantly improved. This improvement in modelled column NO2 is due to better modelled NOy profiles and points to transport errors in the ECMWF ERA-40 reanalyses.

This paper characterizes vertical ozone profiles retrieved with the IMK-IAA (Institute for Meteorology and Climate Research, Karlsruhe – Instituto de Astrofisica de Andalucia) science-oriented processor from high spectral resolution data (until March 2004) measured by the Michelson Interferometer for Passive Atmospheric Sounding (MIPAS) aboard the environmental satellite Envisat. Bias determination and precision validation is performed on the basis of correlative measurements by ground-based lidars, Fourier transform infrared spectrometers, and microwave radiometers as well as balloon-borne ozonesondes, the balloon-borne version of MIPAS, and two satellite instruments (Halogen Occultation Experiment and Polar Ozone and Aerosol Measurement III). Percentage mean differences between MIPAS and the comparison instruments for stratospheric ozone are generally within ±10%. The precision in this altitude region is estimated at values between 5 and 10% which gives an accuracy of 15 to 20%. Below 18 km, the spread of the percentage mean differences is larger and the precision degrades to values of more than 20% depending on altitude and latitude. The main reason for the degraded precision at low altitudes is attributed to undetected thin clouds which affect MIPAS retrievals, and to the influence of uncertainties in the water vapor concentration.

Radiosonde temperature profiles from Belgrano (78° S) and other Antarctic stations have been compared with European Centre for Medium-Range Weather Forecasting (ECMWF) and National Centers for Environmental Prediction (NCEP) operational analyses during the winter of 2003. Results show good agreement between radiosondes and NCEP and a bias in the ECMWF model which is height and temperature dependent, being up to 3°C too cold at 80 and 25–30 hPa, and hence resulting in an overestimation of the predicted potential PSC areas. Here we show the results of the comparison and discuss the potential implications that this bias might have on the ozone depletion computed by Chemical Transport Models based on ECMWF temperature fields, after rejecting the possibility of a bias in the sondes at extreme low temperatures.

Surface ozone and temperature trends were investigated using records from 2000 to 2021 in Southwestern Europe, at El Arenosillo observatory, focusing on June and December. The ozone trends for daily percentiles were increasing in June for lower percentiles (2.5 ± 1.2 ppb decade -1 for the 5th percentile) and decreasing for higher (- 2.2 ± 1.4 ppb decade -1 for the 95th percentile); in December, the trends were growing in the entire range of percentiles, with a peak of 2.2 ± 0.8 ppb decade -1 . A declining trend was obtained for the geopotential height at the pressure level of 850 hPa (Z850) in June while highlighting the upward trend in December (26.3 ± 6.5 m decade -1 ). The hourly trends for ozone and temperature were also explored in these months. In June, the nocturnal ozone trends were growing (4.0 ± 1.2 ppb decade -1 or 10% decade -1 at 8:00 UTC) associated with temperature rises while in the daytime, a decrease in temperature was observed along with an ozone decreasing trend (- 2.6 ± 1.6 ppb decade -1 or - 5% decade -1 at 18:00 UTC). Hourly ozone and temperature trends in December were increasing with peaks of 3.0 ± 0.9 ppb decade -1 (~ 8% decade -1 ) at 12:00 UTC and 1.6 ± 0.3 °C decade -1 at 19:00 UTC. Two representative scenarios of these months were studied. The ozone decreases in June could be associated with several factors, decreasing in temperatures and a possible weakening of the anticyclonic conditions leading to changes in the mesoscale processes' development. The strengthening of the Azores anticyclone in December could be enhancing the upward ozone trend observed. It is unknown whether the reversal ozone pattern trends found in this region are a local phenomenon; although we suggest that it could be happening on a larger scale as well, future studies should be carried out., (© 2024. The Author(s), under exclusive licence to Springer-Verlag GmbH Germany, part of Springer Nature.)

Risk assessment of pesticide impacts on remote ecosystems makes use of model-estimated degradation in air. Recent studies suggest these degradation rates to be overestimated, questioning current pesticide regulation. Here, we investigated the concentrations of 76 pesticides in Europe at 29 rural, coastal, mountain, and polar sites during the agricultural application season. Overall, 58 pesticides were observed in the European atmosphere. Low spatial variation of 7 pesticides suggests continental-scale atmospheric dispersal. Based on concentrations in free tropospheric air and at Arctic sites, 22 pesticides were identified to be prone to long-range atmospheric transport, which included 15 substances approved for agricultural use in Europe and 7 banned ones. Comparison between concentrations at remote sites and those found at pesticide source areas suggests long atmospheric lifetimes of atrazine, cyprodinil, spiroxamine, tebuconazole, terbuthylazine, and thiacloprid. In general, our findings suggest that atmospheric transport and persistence of pesticides have been underestimated and that their risk assessment needs to be improved.

Surface ozone trends observed at El Arenosillo observatory for the last 22 years (2000-2021) were investigated. The trends for daily averages and daily 5th and 95th percentiles were 1.2 ± 0.3 ppb decade -1 , 2.2 ± 0.3 ppb decade -1 and -0.03 ± 0.43 ppb decade -1 , respectively, thus showing a significant increase of background ozone. The surface temperature trends were also explored, obtaining trends of 0.5 ± 0.2 ⁰C decade -1 , 1.1 ± 0.2 ⁰C decade -1 and -0.3 ± 0.2 ⁰C decade -1 for daily averages, 5th and 95th percentiles, respectively. To identify potential changes in the ozone drivers, the weather pattern shifts were analyzed through the horizontal distribution trends of temperature at 2 m and geopotential height at 850 hPa. A strengthening of the Azores anticyclone and a regional warming were detected, which could contribute to the ozone trends obtained. The surface ozone trend in every month was explored, identifying a monthly pattern, with remarkable opposite trends in December-January (2.4 ± 0.9 ppb decade -1 ) vs July-August (-0.5 ± 1.1 ppb decade -1 ). The surface ozone trends for every hour of the day were also explored, identifying two clear patterns. The first pattern occurred from spring to autumn and was characterized by a behavior opposite to the typical daily ozone cycle. The second pattern was observed in winter, and it shows two relative peaks in the ozone trends (around 13:00 and 19:00 UTC). In a context of ozone precursor's depletion, changes in the weather conditions and warmer climate, to improve our knowledge of the ozone trends, we suggest exploring them based on daily and hourly averages., (Copyright © 2022 Elsevier Inc. All rights reserved.)

The Radiation and Dust Sensor is one of six sensors of the Mars Environmental Dynamics Analyzer onboard the Perseverance rover from the Mars 2020 NASA mission. Its primary goal is to characterize the airbone dust in the Mars atmosphere, inferring its concentration, shape and optical properties. Thanks to its geometry, the sensor will be capable of studying dust-lifting processes with a high temporal resolution and high spatial coverage. Thanks to its multiwavelength design, it will characterize the solar spectrum from Mars' surface. The present work describes the sensor design from the scientific and technical requirements, the qualification processes to demonstrate its endurance on Mars' surface, the calibration activities to demonstrate its performance, and its validation campaign in a representative Mars analog. As a result of this process, we obtained a very compact sensor, fully digital, with a mass below 1 kg and exceptional power consumption and data budget features.

Predicting radiative forcing due to Antarctic stratospheric ozone recovery requires detecting changes in the ozone vertical distribution. In this endeavor, the Limb Profiler of the Ozone Mapping and Profiler Suite (OMPS-LP), aboard the Suomi NPP satellite, has played a key role providing ozone profiles over Antarctica since 2011. Here, we compare ozone profiles derived from OMPS-LP data (version 2.5 algorithm) with balloon-borne ozonesondes launched from 8 Antarctic stations over the period 2012-2020. Comparisons focus on the layer from 12.5 to 27.5 km and include ozone profiles retrieved during the Sudden Stratospheric Warming (SSW) event registered in Spring 2019. We found that, over the period December-January-February-March, the root mean square error (RMSE) tends to be larger (about 20%) in the lower stratosphere (12.5-17.5 km) and smaller (about 10%) within higher layers (17.5-27.5 km). During the ozone hole season (September-October-November), RMSE values rise up to 40% within the layer from 12.5 to 22 km. Nevertheless, relative to balloon-borne measurements, the mean bias error of OMPS-derived Antarctic ozone profiles is generally lower than 0.3 ppmv, regardless of the season.

Eleven years, January 2008 to June 2019, of hourly nitrogen dioxide (NO 2 ) levels recorded at El Arenosillo observatory (Southwestern Europe) were analyzed. Annual averages ranged between 4 μg m -3 and 6 μg m -3 with peaks exceeding 40 μg m -3 . A slight monthly variation was observed with maximum and minimum values in the cold (∼6 μg m -3 ) and warm (∼4 μg m -3 ) seasons respectively. A diurnal pattern was found with a weak amplitude (∼3 μg m -3 ). The monthly trends were investigated using surface observations and OMI (Ozone Monitoring instrument) satellite measurements. An unexpected upward trend was obtained in the last five years. The periods with elevated NO 2 concentrations in the last years were analyzed, showing an increase in its frequency and concentrations, linked with the upward trend observed. The weather conditions in these NO 2 peaks were studied using local surface meteorology, mean sea level pressure and wind fields from the data reanalysis of ERA5. The transport of NO 2 was explored using TROPOMI (Tropospheric Monitoring Instrument) measurements. The events occurred under conditions governed by high-pressure systems, which induced weak synoptic airflows or the development of mesoscale processes. Four scenarios of NO 2 transport were identified, associated with weak synoptic flows from inland or Southern Portugal and with mesoscale processes. The gulf of Cadiz plays an important role as a reservoir where the NO 2 coming from the south of Portugal, the Western Mediterranean Basin and urban-industrial areas can be accumulated and later transported inland. A strong correlation was found between the increase of NO 2 observed in the last years and positive anomalies of the temperature and geopotential height at 850 and 500 hPa levels. These findings could indicate that the causes of the changes in the NO 2 would be attributed to alterations in the weather patterns associated with a warmer climate., (Copyright © 2020 Elsevier Ltd. All rights reserved.)

Two years of SO 2 measurements at El Arenosillo observatory located in the Gulf of Cadiz (Atlantic Ocean) were investigated. Annual hourly averages of 1.9 ± 1.5 μg m - and p95 between 3 and 4.4 μg m 3 were recorded, showing clean and background environments. Monthly means vary between 1.5 and 2.4 μg m - 3 were recorded, showing clean and background environments. Monthly means vary between 1.5 and 2.4 μg m - 3 , a monthly evolution was not found. SO 2 increases were observed in specific periods. A selection methodology was applied to extract these events, which showed a mean of ~11 μg m 2 sources and its transport, which could be affecting the studied region. Although SO 2 records were low, major conductive for SO 2 increases were observed in specific periods. A selection methodology was applied to extract these events, which showed a mean of ~11 μg m - 3 . Surface meteorological observations and ERA5 meteorological fields from the ECMWF model were used to assess the weather conditions. SO 2 increases, in cold months occurred under conditions governed by synoptic-scale. Two types of transport scenarios were identified: SO 2 transport defined as direct impact, which is the sum of the plumes from Portugal and the Huelva area; and indirect impact, where SO 2 and sulphate particle emissions from Portugal were transported and accumulated in the Gulf of Cadiz and then carried inland, where new particle formation were observed. Episodes with high SO 2 concentrations were also reported in warm periods associated with pure sea-land breezes. The SO 2 peaks under sea-land breezes were associated with the transport of SO 2 from the south of Portugal to the Gulf of Cadiz, whereas SO 2 from the east of the Iberian Peninsula and north of Africa reached the Mediterranean Sea and were then transported to the Atlantic Ocean following the Strait of Gibraltar. Blocking of the airflows from the Mediterranean Sea to the Atlantic Ocean turns the Gulf of Cadiz into a chemical reservoir, where chemical species such as SO 2 can accumulate, triggering new particle formation processes., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2020 Elsevier B.V. All rights reserved.)