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The catalytic influence of water molecules on BrO + CH2O reaction was discussed through the investigation of mechanism and kinetics. The potential energy surfaces and dynamic properties of the BrO + CH2O reaction were investigated at the CCSD(T)/aug-cc-pVTZ//B3LYP/cc-pVTZ level. The reaction generates four different products, respectively, through four pathways without water and nine pathways with water. The results have shown that the generation of HCO + HOBr occupied the entire reaction without water. The rate constants were obtained by employing the KisThelP program based on the Transition State Theory with Wigner tunneling correction. This rate constants of the naked reaction are lower than that in the presence of monomolecular water and are higher than that in the presence of bimolecular water. The current calculations indicated that monomolecular water could accelerate the BrO + CH2O reaction, while bimolecular water could not accelerate the BrO + CH2O reaction. The effective rate constants (in the presence of monomolecular water and bimolecular water) are much lower than that of the naked reaction. [ABSTRACT FROM AUTHOR]

Denitrification of the stratospheric vortex is a crucial process for the Antarctic Ozone Hole formation resulting in an analogous stratospheric "Nitrogen Hole". Here, 2018–2021 daily TROPOMI measurements are used for the first time for a detailed characterization of this Nitrogen Hole. Nitrogen dioxide total columns exhibit strong spatiotemporal and seasonal variations associated with both photochemistry as well as transport and mixing processes. Combined with total ozone column data two main regimes are identified: inner-vortex ozone and nitrogen dioxide depleted air and outer-vortex air enhanced in ozone and nitrogen dioxide. Within the vortex total ozone and total stratospheric nitrogen dioxide are strongly correlated which is much less evident outside of the vortex. Connecting both main regimes are what is defined here as "mixing lines", a third regime of coherent patterns in the total nitrogen dioxide column – total ozone column phase space. These mixing lines exist because of differences in three dimensional variations of nitrogen dioxide and ozone thereby providing information about vortex dynamics and cross-vortex edge mixing. On the other hand, interannual variability of nitrogen dioxide – total ozone characteristics are rather small except in 2019 when the vortex was unusually unstable. Overall, the results show that daily stratospheric nitrogen dioxide column satellite measurements provide an innovative means for characterizing and Polar stratospheric denitrification processes and vortex dynamics and potentially long term monitoring if the total nitrogen column data record is extended with past satellite observations. [ABSTRACT FROM AUTHOR]

Year‐round precipitation in coastal East Antarctica and Antarctic Peninsula was used to investigate the seasonal patterns in sources of atmospheric perchlorate (ClO4− ${{\text{ClO}}_{4}}^{-}$). Although featuring distinct climates, the two locations exhibit similar annual mean and seasonal cycles of ClO4− ${{\text{ClO}}_{4}}^{-}$ concentration, with higher values in autumn and lower concentrations in winter and spring. Tropospheric formation dominates atmospheric ClO4− ${{\text{ClO}}_{4}}^{-}$ in spring and summer, which is influenced by both oxidants levels and environmental conditions (e.g., air humidity). Tropospheric ClO4− ${{\text{ClO}}_{4}}^{-}$ production may also be promoted by elevated levels of oxidants brought by air mass from the interior Antarctic ice sheet in spring and summer. The autumn concentration maximum may originate from ClO4− ${{\text{ClO}}_{4}}^{-}$ produced in the stratosphere through reactions between reactive chlorine and ozone during spring and summer. In winter, the stratospheric input may contribute to ClO4− ${{\text{ClO}}_{4}}^{-}$ via polar stratospheric clouds sedimentation. Plain Language Summary: Perchlorate (ClO4− ${{\text{ClO}}_{4}}^{-}$) is an inorganic anion with a persistent presence in the environment, where its exposure can pose a significant health risk to humans. Environmental ClO4− ${{\text{ClO}}_{4}}^{-}$ is derived from both man‐made and natural sources. Natural ClO4− ${{\text{ClO}}_{4}}^{-}$, widespread in the environment, is thought to be formed in the atmosphere. However, knowledge on the sources and, in particular, the formation mechanisms of natural ClO4− ${{\text{ClO}}_{4}}^{-}$ is quite limited. Antarctica, with negligible man‐made sources, is one of the best regions for investigations on natural ClO4− ${{\text{ClO}}_{4}}^{-}$. Year‐round precipitation samples were collected at China Zhongshan Station located in coastal East Antarctica and China Great Wall Station on King George Island, Antarctic Peninsula. Results show that atmospheric ClO4− ${{\text{ClO}}_{4}}^{-}$ concentration presents obvious seasonal cycles, which are related to variations in sources. A significant amount of ClO4− ${{\text{ClO}}_{4}}^{-}$ is associated with tropospheric chemistry in spring and summer. Precursor levels, environmental conditions, and air mass from the interior Antarctica may influence tropospheric ClO4− ${{\text{ClO}}_{4}}^{-}$ formation. The maximum concentration in autumn may originate from ClO4− ${{\text{ClO}}_{4}}^{-}$ formed in the stratosphere during spring and summer, and the stratospheric input may also contribute to atmospheric ClO4− ${{\text{ClO}}_{4}}^{-}$ in winter. Key Points: Antarctic atmospheric perchlorate (ClO4− ${{\text{ClO}}_{4}}^{-}$) concentration at different locations exhibits a clear seasonal cycleThe highest concentration in autumn is likely related to ClO4− ${{\text{ClO}}_{4}}^{-}$ produced in the stratosphere in spring and summerMajor source of ClO4− ${{\text{ClO}}_{4}}^{-}$ in spring and summer is tropospheric formation influenced by both oxidants and environmental conditions [ABSTRACT FROM AUTHOR]

2D and quasi-2D hybrid perovskites have been in the spotlight for the past few years due to their generally enhanced environmental stability compared to their 3D counterparts and a much higher degree of compositional and structural flexibility. Incorporating organic cations with an extended conjugated system presents a sub-field of research that is gaining increasing attention due to the potential of creating hybrids with new and improved material properties. This includes the emergence of charge- and energy-transfer processes between the organic and inorganic layers, enhanced charge carrier transport, reduced exciton binding energy, and superior stability. However, incorporating organic cations with an extended conjugated system generates additional challenges. The processing of thin films as well as the growth of single crystals needs to be optimised. Control over the crystal structure obtained from the precursor components under the conditions for thin film deposition and crystal growth needs to be achieved. The rational design of the molecular structure of the organic cation in combination with a specific inorganic framework to achieve the desired properties presents the final challenge. In this perspective, we provide a critical analysis of the opportunities and challenges associated with the use of conjugated organic cations in 2D and quasi-2D hybrid perovskites. [ABSTRACT FROM AUTHOR]

The Arctic stratospheric ozone depletion event in spring 2020 was the most severe compared with previous years. We retrieved the critical indicator ozone vertical column density (VCD) using zenith scattered light differential optical absorption spectroscopy (ZSL-DOAS) from March 2017 to September 2021 in Ny-Ålesund, Svalbard, Norway. The average ozone VCD over Ny-Ålesund between 18 March and 18 April 2020 was approximately 274.8 Dobson units (DU), which was only 64.7 ± 0.1% of that recorded in other years (2017, 2018, 2019, and 2021). The daily peak difference was 195.7 DU during this period. The retrieved daily averages of ozone VCDs were compared with satellite observations from the Global Ozone Monitoring Experiment-2 (GOME-2), a Brewer spectrophotometer, and a Système d'Analyze par Observation Zénithale (SAOZ) spectrometer at Ny-Ålesund. As determined using the empirical cumulative density function, ozone VCDs from the ZSL-DOAS dataset were strongly correlated with data from the GOME-2 and SAOZ at lower and higher values, and ozone VCDs from the Brewer instrument were overestimated. The resulting Pearson correlation coefficients were relatively high at 0.97, 0.87, and 0.91, respectively. In addition, the relative deviations were 2.3%, 3.1%, and 3.5%, respectively. Sounding and ERA5 data indicated that severe ozone depletion occurred between mid-March and mid-April 2020 in the 16–20 km altitude range over Ny-Ålesund, which was strongly associated with the overall persistently low temperatures in the winter of 2019/2020. Using ZSL-DOAS observations, we obtained ozone VCDs and provided evidence for the unprecedented ozone depletion during the Arctic spring of 2020. This is essential for the study of polar ozone changes and their effect on climate change and ecological conditions. [ABSTRACT FROM AUTHOR]

Compared to 3D perovskites, 2D perovskites exhibit excellent stability, structural diversity, and tunable bandgaps, making them highly promising for applications in solar cells, light-emitting diodes, and photodetectors. However, the trade-off for worse charge transport is a critical issue that needs to be addressed. This comprehensive review first discusses the structure of 3D and 2D metal halide perovskites, then summarizes the significant factors influencing charge transport in detail and provides a brief overview of the testing methods. Subsequently, various strategies to improve the charge transport are presented, including tuning A'-site organic spacer cations, A-site cations, B-site metal cations, and X-site halide ions. Finally, an outlook on the future development of improving the 2D perovskites' charge transport is discussed., (© 2024 Wiley‐VCH GmbH.)

Volatile organic compounds (VOCs) are key precursors of particulate matter and tropospheric ozone. Although the terrestrial biosphere is by far the largest source of VOCs into the atmosphere, the emissions of biogenic VOCs remain poorly constrained at regional scale. In this work, we derive top-down biogenic emissions over Europe using weekly-averaged TROPOMI formaldehyde (HCHO) data from 2018 to 2021. The systematic bias of the TROPOMI HCHO columns is characterized and corrected for based on comparisons with FTIR data at seven European stations. The top-down fluxes of biogenic, pyrogenic, and anthropogenic VOC sources are optimized using an inversion framework based on the MAGRITTEv1.1 chemistry transport model and its adjoint. The inversion leads to strongly increased isoprene emissions with respect to the MEGAN-MOHYCAN inventory over the model domain (from 8.1 to 18.5 Tg yr-1) which is driven by the high observed TROPOMI HCHO columns in southern Europe. The impact of the inversion on biomass burning VOCs (+13 %) and anthropogenic VOCs (-17 %) is moderate. An evaluation of the optimized HCHO distribution against ground-based remote sensing (FTIR and MAX-DOAS) and in situ data provides generally improved agreement at stations below about 50° N, but indicates overestimated emissions in northern Scandinavia. Sensitivity inversions show that the top-down emissions are robust with respect to changes in the inversion settings and in the model chemical mechanism. However, the top-down emissions are very sensitive to the bias correction of the observed columns. Furthermore, the use of different a priori emissions has a significant impact on the inversion results due to large differences among bottom-up inventories. In regions with variable meteorology, there is strong week-to-week variability in the observed HCHO columns. The top-down emissions, which are optimized at weekly increments, have a much improved capability of representing these large fluctuations than an inversion using monthly increments. [ABSTRACT FROM AUTHOR]

The TRacking Aerosol Convection ExpeRiment – Air Quality (TRACER-AQ) campaign probed Houston air quality with a comprehensive suite of ground-based and airborne remote sensing measurements during the intensive operating period in September 2021. Two post-frontal high-ozone episodes (6–11 and 23–26 September) were recorded during the aforementioned period. In this study, we evaluated the simulation of the planetary boundary layer (PBL) height and the vertical ozone profile by a high-resolution (1.33 km) 3-D photochemical model, the Weather Research and Forecasting (WRF)-driven GEOS-Chem (WRF-GC). We evaluated the PBL heights with a ceilometer at the coastal site La Porte and the airborne High Spectral Resolution Lidar 2 (HSRL-2) flying over urban Houston and adjacent waters. Compared with the ceilometer at La Porte, the model captures the diurnal variations in the PBL heights with a very strong temporal correlation (R>0.7) and ±20 % biases. Compared with the airborne HSRL-2, the model exhibits a moderate to strong spatial correlation (R=0.26 –0.68), with ±20 % biases during the noon and afternoon hours during ozone episodes. For land–water differences in PBL heights, the water has shallower PBL heights compared to land. The model predicts larger land–water differences than the observations because the model consistently underestimates the PBL heights over land compared to water. We evaluated vertical ozone distributions by comparing the model against vertical measurements from the TROPospheric OZone lidar (TROPOZ), the HSRL-2, and ozonesondes, as well as surface measurements at La Porte from a model 49i ozone analyzer and one Continuous Ambient Monitoring Station (CAMS). The model underestimates free-tropospheric ozone (2–3 km aloft) by 9 %–22 % but overestimates near-ground ozone (<50 m aloft) by 6 %-39 % during the two ozone episodes. Boundary layer ozone (0.5–1 km aloft) is underestimated by 1 %–11 % during 8–11 September but overestimated by 0 %–7 % during 23–26 September. Based on these evaluations, we identified two model limitations, namely the single-layer PBL representation and the free-tropospheric ozone underestimation. These limitations have implications for the predictivity of ozone's vertical mixing and distribution in other models. [ABSTRACT FROM AUTHOR]

During polar spring, ozone depletion events (ODEs) are often observed in combination with bromine explosion events (BEEs) in Ny-Ålesund. In this study, two long-term ozone data sets (2010–2021) from ozonesonde launches and in situ ozone measurements have been evaluated between March and May of each year to study ODEs in Ny-Ålesund. Ozone concentrations below 15 ppb were marked as ODEs. We applied a composite analysis to evaluate tropospheric BrO retrieved from satellite data and the prevailing meteorological conditions during these events. During ODEs, both data sets show a blocking situation with a low-pressure anomaly over the Barents Sea and anomalously high pressure in the Icelandic Low area, leading to transport of cold polar air from the north to Ny-Ålesund with negative temperature and positive BrO anomalies found around Svalbard. In addition, a higher wind speed and a higher, less stable boundary layer are noticed, supporting the assumption that ODEs often occur in combination with polar cyclones. Applying a 20 ppb ozone threshold value to tag ODEs resulted in only a slight attenuation of the BrO and meteorological anomalies compared to the 15 ppb threshold. Monthly analysis showed that BrO and meteorological anomalies are weakening from March to May. Therefore, ODEs associated with low-pressure systems, high wind speeds, and blowing snow more likely occur in early spring, while ODEs associated with low wind speed and stable boundary layer meteorological conditions seem to occur more often in late spring. Annual evaluations showed similar weather patterns for several years, matching the overall result of the composite analysis. However, some years show different meteorological patterns deviating from the results of the mean analysis. Finally, an ODE case study from the beginning of April 2020 in Ny-Ålesund is presented, where ozone was depleted for 2 consecutive days in combination with increased BrO values. The meteorological conditions are representative of the results of the composite analysis. A low-pressure system arrived from the northeast to Svalbard, resulting in high wind speeds with blowing snow and transport of cold polar air from the north. [ABSTRACT FROM AUTHOR]

Observations of nitrogen dioxide (NO2) and nitrogen oxide (NO) in the stratosphere are relevant to understand long-term changes and variabilities in stratospheric nitrogen oxide (NOx) and ozone (O3) concentrations. Due to the versatile role of NO2 and NO in stratospheric O3 photochemistry they are important for recovery and build-up of O3 holes in the stratosphere, and therefore can indirectly affect the human life. Thus, we present in this work the evaluation of NO2 and NO stratospheric partial columns (> 16 km altitude) retrieved from ground-based Fourier-transform infrared (FTIR) measurements from over 25 years at Zugspitze (47.42° N, 10.98° E, 2964 m a.s.l.) and 18 years at Garmisch (47.47° N, 11.06° E, 745 m a.s.l.), Germany. The obtained stratospheric columns are only weakly influenced by tropospheric pollution and show only a very small bias of (2.5±0.2) % when comparing NO2 above Zugspitze and Garmisch. Stratospheric columns of both NO2 and NO show a diurnal increase in dependence of local solar time (LST). We quantified this behavior by calculating diurnal increasing rates. Here, we find mean values for the NO2 diurnal increasing rate of (0.89±0.14)·1014 cm-2 h-1 and (0.94±0.14)·1014 cm-2 h-1 at Zugspitze and Garmisch, respectively. The mean NO a.m. diurnal increasing rate above Zugspitze can be found to be (1.42±0.12)·1014 cm-2 h-1. Regarding the seasonal dependency of these increasing rates, for the first time, we were able to detect a significant seasonal variation of both NO2 diurnal increasing rates and NO a.m. diurnal increasing rates experimentally with a maximum of (1.13±0.04)·1014 cm-1 h-1 for NO2 and (1.76±0.25)·1014 cm-1 h-1 for NO in September and a minimum of (0.71±0.18)·1014 cm-1 h-1 in December for NO2 and a minimum of (1.18±0.41)·1014 cm-1 h-1 in November for NO. This similar behavior may be explained by the interconnection of both species in stratospheric photochemistry. The outcome of this work is a retrieval and analyzation strategy of FTIR data for NOx stratospheric columns, which can help to further validate photochemical models or improve satellite validations. The first use of this data set is shown in a companion paper (Nürnberg et al., 2023) extracting experiment-based NOx scaling factors describing the diurnal increase out of the retrieved partial columns and validating recently published model-based scaling factors. [ABSTRACT FROM AUTHOR]

The Geostationary Environmental Monitoring Spectrometer (GEMS) is a UV-visible (UV-Vis) spectrometer on board the GEO-KOMPSAT-2B (Geostationary Korea Multi-Purpose Satellite 2B) satellite launched into a geostationary orbit in February 2020. To evaluate the GEMS NO 2 total column data, a comparison was carried out using the NO 2 vertical column density (VCD) that measured direct sunlight using the Pandora spectrometer system at four sites in Seosan, South Korea, from November 2020 to January 2021. Correlation coefficients between GEMS and Pandora NO 2 data at four sites ranged from 0.35 to 0.48, with root mean square errors (RMSEs) from 4.7×1015 to 5.5×1015 molec. cm -2 for a cloud fraction (CF) <0.7. Higher correlation coefficients of 0.62–0.78 with lower RMSEs from 3.3×1015 to 5.0×1015 molec. cm -2 were found with CF <0.3 , indicating the higher sensitivity of GEMS to atmospheric NO 2 in less cloudy conditions. Overall, the GEMS NO 2 total column data tended to be lower than the Pandora data, owing to differences in the representative spatial coverage, with a large negative bias under high CF conditions. With a correction for horizontal representativeness in the Pandora measurement coverage, correlation coefficients ranging from 0.69 to 0.81, with RMSEs from 3.2×1015 to 4.9×1015 molec. cm -2 , were achieved for CF <0.3 , showing a better correlation with the correction than without the correction. [ABSTRACT FROM AUTHOR]

During polar spring, periods of elevated tropospheric bromine drive near complete removal of surface ozone. These events impact the tropospheric oxidative capacity and are an area of active research with multiple approaches for representing the underlying processes in global models. We present a method for parameterizing emissions of molecular bromine (Br2) over the Arctic using satellite retrievals of bromine monoxide (BrO) from the Ozone Monitoring Instrument (OMI). OMI retrieves column BrO with daily near global coverage, and we use the GEOS‐Chem chemical mechanism, run online within the Goddard Earth Observing System Earth System Model to identify hotspots of BrO likely associated with polar processes. To account for uncertainties in modeling background BrO, hotspots are only identified where the difference between OMI and modeled columns exceeds a statistical threshold. The resulting hotspot columns are a lower‐limit for the portion of OMI BrO attributable to bromine explosion events. While these hotspots are correlated with BrO measured in the lower troposphere over the Arctic Ocean, a case study of missing detections of near‐surface BrO is identified. Daily flux of Br2 is estimated from hotspot columns of BrO using internal model parameters. When the emissions are applied, BrO hotspots are modeled with a 5% low bias. The sensitivity of the resulting ozone simulations to the treatment of background uncertainties in the BrO column is demonstrated. While periods of isolated, large (>50%) decreases in surface ozone are modeled, this technique does not simulate the low ozone observed at coastal stations and consistently underestimates ozone loss during March. Plain Language Summary: During polar spring, high levels of bromine‐containing molecules drive near complete removal of surface ozone (O3), impacting the chemistry of the troposphere and the biological uptake of mercury. Global models currently have multiple mechanisms for representing the underlying processes that produce brominated molecules in polar regions. We estimate molecular bromine (Br2) emissions from measurements of bromine monoxide (BrO) collected over the Arctic by a satellite instrument. An atmospheric model, run without polar emissions of Br2, is used to estimate how much of the satellite BrO signal is due to background processes in the stratosphere and troposphere and isolate the portion of the signal likely associated with Arctic emissions. We account for uncertainties in the model representation of background BrO using a statistical threshold. Because of the catalytic nature of bromine‐mediated ozone depletion, we focus our initial efforts on developing a lower‐limit estimate of Arctic emissions. The amount of BrO attributed to polar processes and the resulting impact on O3 are sensitive to the magnitude of the statistical threshold, with a better representation of surface O3 achieved with a lower threshold. While the satellite‐based emissions result in periodic decreases in surface O3 in late spring, modeled O3 is consistently high with respect to observations, particularly during early spring. Key Points: BrO hotspots are isolated from satellite signals using modeled columns of BrO and a bias threshold to account for model uncertaintiesWe estimate Arctic Br2 emissions from BrO signals and demonstrate the sensitivity of modeled O3 to the BrO hotspot detection thresholdSimulations with satellite‐based Br2 emissions overestimate springtime Arctic surface O3 with few ozone depleting events modeled in March [ABSTRACT FROM AUTHOR]

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The atmospheric chemistry of halogenated species (Cl, Br, I) participates in the global chemical sink of tropospheric ozone and perturbs the oxidising capacity of the troposphere, notably by influencing the atmospheric lifetime of methane. Global chemistry–climate models are commonly used to assess the global budget of ozone and its sensitivity to emissions of its precursors, as well as to project its long-term evolution. Here, we report on the implementation of tropospheric sources and chemistry of halogens in the chemistry–climate model LMDZ-INCA (Laboratoire de Météorologie Dynamique general circulation model, LMDZ, and Interactions with Chemistry and Aerosols, INCA, version with Non-Methane HydroCarbon chemistry, vNMHC) and evaluate halogen effects on the tropospheric ozone budget. Overall, the results show that the model simulates satisfactorily the impact of halogens on the photo-oxidising system in the troposphere, in particular in the marine boundary layer. To quantify the effects of halogen chemistry in LMDZ-INCA, standard metrics representative of the behaviour of the tropospheric chemical system (O x , HO x , NO x , CH 4 and non-methane volatile organic compounds – NMVOCs) are computed with and without halogens. The addition of tropospheric halogens in the LMDZ-INCA model leads to a decrease of 22 % in the ozone burden, 8 % in OH and 33 % in NO x. Sensitivity simulations show for the first time that the inclusion of halogen chemistry makes ozone more sensitive to perturbations in CH 4 , NO x and NMVOCs. Consistent with other global model studies, the sensitivity of the tropospheric ozone burden to changes from pre-industrial to present-day emissions is found to be ∼20 % lower when tropospheric halogens are taken into account. [ABSTRACT FROM AUTHOR]

Reactive halogen chemistry in the springtime Arctic causes ozone depletion events and alters the rate of pollution processing. There are still many uncertainties regarding this chemistry, including the multiphase recycling of halogens and how sea ice impacts the source strength of reactive bromine. Adding to these uncertainties are the impacts of a rapidly warming Arctic. We present observations from the CHemistry in the Arctic: Clouds, Halogens, and Aerosols (CHACHA) field campaign based out of Utqiag ̇vik, Alaska from mid-February to mid-April of 2022 to provide information on the vertical distribution of bromine monoxide (BrO), which is a tracer for reactive bromine chemistry. Data was gathered using the Heidelberg Airborne Imaging DOAS Instrument (HAIDI) on the Purdue University Airborne Laboratory for Atmospheric Research (ALAR) and employing a unique sampling technique of vertically profiling the lower atmosphere with the aircraft via 'porpoising' ma- neuvers. Observations from HAIDI were coupled with radiative transfer model calculations to retrieve mixing ratio profiles throughout the lower atmosphere (below 1000 m), with unprecedented vertical resolution (50 m) and total information gathered (average of 17.5 degrees of freedom) for this region. A cluster analysis was used to categorize 245 retrieved BrO mixing ratio vertical profiles into four common profile shapes. We often found the highest BrO mixing ratios at the Earth's surface with a mean of nearly 30 pmol mol−1 in the lowest 50 m, indicating an important role for multiphase chemistry on the snowpack in reactive bromine production. Most lofted BrO profiles corresponded with an aerosol profile that peaked at the same altitude (225 m above the ground), suggesting that BrO was maintained due to heterogeneous reactions on particle surfaces aloft during these cases. A majority, 11 of 15, of the identified lofted BrO cases occurred on a single day, March 19, 2022, over an area covering more than 24,000 km2, indicating that this was a large scale lofted BrO event. The clustered BrO mixing ratio profiles should be particularly useful for MAX-DOAS studies, where prior BrO profiles, needed for the optimal estimation retrieval, are not often based on previous observations. Future MAX-DOAS studies (and past reanalyses) could rely on the profiles provided in this work to improve BrO retrievals. [ABSTRACT FROM AUTHOR]

Heatwaves are a substantial health threat in the UK, exacerbated by co-occurrence of ozone pollution episodes. Here we report on the first use of retrieved vertical profiles of nitrogen dioxide (NO2) and formaldehyde (HCHO) over Central London from a newly installed multi-axis differential optical absorption spectroscopy (MAX-DOAS) instrument coincident with two of three heatwaves for the hottest summer on record. We evaluate space-based sensor observations routinely used to quantify temporal changes in air pollution and precursor emissions over London. Collocated daily mean tropospheric column densities from the high-spatial-resolution space-based TROPOspheric Monitoring Instrument (TROPOMI) and MAX-DOAS, after accounting for differences in vertical sensitivities, are temporally consistent for NO2 and HCHO (both R = 0.71). TROPOMI NO2 is 27 %–31 % less than MAX-DOAS NO2 , as expected from horizontal dilution of NO2 by TROPOMI pixels in polluted cities. TROPOMI HCHO is 20 % more than MAX-DOAS HCHO , greater than differences in past validation studies but within the range of systematic errors in the MAX-DOAS retrieval. The MAX-DOAS near-surface (0–110 m) retrievals have similar day-to-day and hourly variability to the surface sites for comparison of NO2 (R ≥ 0.7) and for MAX-DOAS HCHO versus surface site isoprene (R ≥ 0.7) that oxidises to HCHO in prompt and high yields. Daytime ozone production, diagnosed with MAX-DOAS HCHO -to- NO2 tropospheric vertical column ratios, is mostly limited by availability of volatile organic compounds (VOCs), except on heatwave days. Temperature-dependent biogenic VOC emissions of isoprene increase exponentially, resulting in ozone concentrations that exceed the regulatory standard for ozone and cause non-compliance at urban background sites in Central London. Locations in Central London heavily influenced by traffic remain in compliance, but this is likely to change with stricter controls on vehicle emissions of NOx and higher likelihood of heatwave frequency, severity, and persistence due to anthropogenic climate change. [ABSTRACT FROM AUTHOR]

The angular distribution of the sky radiance determines the energy generation of solar power technologies as well as the ultraviolet (UV) doses delivered to the biosphere. The sky-diffuse radiance distribution depends on the wavelength, the solar elevation, and the atmospheric conditions. Here, we report on ground-based measurements of the all-sky radiance at three sites in the Southern Hemisphere across a transect of about 5,000 km: Santiago (33°S, a mid-latitude city of 6 million inhabitants with endemic poor air quality), King George Island (62°S, at the northern tip of the Antarctic Peninsula, one of the cloudiest regions on Earth), and Union Glacier (79°S, a snow-covered glacier in the vast interior of Western Antarctica). The sites were strategically selected for studying the influence of urban aerosols, frequent and thick clouds, and extremely high albedo on the sky-diffuse radiance distribution. Our results show that, due to changing site-specific atmospheric conditions, the characterization of the weather-driven sky radiance distribution may require ground-based measurements. [ABSTRACT FROM AUTHOR]

Quantifying the global bromine monoxide (BrO) budget is essential to understand ozone chemistry better. In particular, the tropospheric BrO budget has not been well characterized. Here, we retrieve nearly a decade (February 2012–July 2021) of stratospheric and tropospheric BrO vertical columns from the Ozone Mapping and Profiling Suite Nadir Mapper (OMPS-NM) onboard the Suomi National Polar-orbiting Partnership (Suomi-NPP) satellite. To address the mismatch between a priori profiles and column retrievals in the stratosphere-troposphere separation, for each OMPS-NM pixel, we save two types of BrO vertical profiles and use the appropriate one based on whether a tropospheric enhancement is detected. Total ozone columns observed from OMPS-NM are used to identify tropospheric BrO enhancements. We demonstrate good agreement for both the stratosphere (r = 0.81–0.83) and the troposphere (r = 0.50–0.69) by comparing monthly mean BrO vertical columns from OMPS-NM with ground-based observations from three stations (Lauder, Utqiag ̇vik, and Harestua). The OMPS-NM BrO retrievals successfully capture tropospheric enhancements not only in the polar but also in the extrapolar regions (the Rann of Kutch and the Great Salt Lake). We also estimate random uncertainties in the retrievals pixel by pixel, which can assist in quantitative applications of the OMPS-NM BrO dataset. Our BrO retrieval algorithm is designed for cross-sensor applications and can be adapted to other space-borne ultraviolet spectrometers, contributing to the creation of continuous long-term satellite BrO observation records. [ABSTRACT FROM AUTHOR]

The sensitivity of satellites to air pollution close to the sea surface is decreased by scattering of light in the atmosphere and low sea surface albedo. To reliably retrieve tropospheric nitrogen dioxide (NO2) columns using the TROPOspheric Monitoring Instrument (TROPOMI), it is therefore necessary to have good a priori knowledge of the vertical distribution of NO2. In this study, we use an aircraft of the Royal Belgian Institute of Natural Sciences, which was already equipped with a sniffer sensor system, measuring NO x (= NO + NO2), CO2 and SO2. This instrumentation enables us to evaluate vertical profile shapes from several chemical transport models and to validate TROPOMI tropospheric NO2 columns over the polluted North Sea in the summer of 2021.We observe multiple clear signatures of ship plumes from seconds after emission to multiple kilometers downwind. Besides that, our results show that the chemical transport model TM5-MP, which is used in the retrieval of the operational TROPOMI NO2 data, tends to underestimate surface level pollution while overestimating NO2 at higher levels over the study region. The higher horizontal resolution in the regional CAMS ensemble mean and LOTOS-EUROS model improve the surface level pollution estimates, but the models still systematically overestimate NO2 levels at higher altitudes, indicating exaggerated vertical mixing in the models over the North Sea. When replacing the TM5 a priori NO2 profiles with the aircraft-measured NO2 profiles in the air mass factor (AMF) calculation, we find smaller recalculated AMFs. Subsequently, the retrieved NO2 columns increase by 20 %, indicating a significant negative bias in the operational TROPOMI NO2 data product (up to v2.3.1) over the North Sea. This negative bias has important implications for estimating emissions over the sea. While TROPOMI NO2 negative biases caused by the TM5 a priori profiles have also been reported over land, the reduced vertical mixing and smaller surface albedo over sea makes this issue especially relevant over sea and coastal regions. [ABSTRACT FROM AUTHOR]

Despite its importance in controlling the abundance of methane (CH 4) and a myriad of other tropospheric species, the hydroxyl radical (OH) is poorly constrained due to its large spatial heterogeneity and the inability to measure tropospheric OH with satellites. Here, we present a methodology to infer tropospheric column OH (TCOH) in the tropics over the open oceans using a combination of a machine learning model, output from a simulation of the GEOS model, and satellite observations. Our overall goals are to assess the feasibility of our methodology, to identify potential limitations, and to suggest areas of improvement in the current observational network. The methodology reproduces the variability of TCOH from independent 3D model output and of observations from the Atmospheric Tomography mission (ATom). While the methodology also reproduces the magnitude of the 3D model validation set, the accuracy of the magnitude when applied to observations is uncertain because current observations are insufficient to fully evaluate the machine learning model. Despite large uncertainties in some of the satellite retrievals necessary to infer OH, particularly for NO 2 and formaldehyde (HCHO), current satellite observations are of sufficient quality to apply the machine learning methodology, resulting in an error comparable to that of in situ OH observations. Finally, the methodology is not limited to a specific suite of satellite retrievals. Comparison of TCOH determined from two sets of retrievals does show, however, that systematic biases in NO 2 , resulting both from retrieval algorithm and instrumental differences, lead to relative biases in the calculated TCOH. Further evaluation of NO 2 retrievals in the remote atmosphere is needed to determine their accuracy. With slight modifications, a similar methodology could likely be expanded to the extratropics and over land, with the benefits of increasing our understanding of the atmospheric oxidation capacity and, for instance, informing understanding of recent CH 4 trends. [ABSTRACT FROM AUTHOR]

The Ozone Mapping and Profiler Suite (OMPS) has been on board the Suomi National Polar-orbiting Partnership (S-NPP) satellite since October 2011 and was followed by an OMPS on NOAA-20 (N20) in November 2017 as part of the US Joint Polar Satellite System (JPSS) program. The OMPS measurements are processed to yield various products of atmospheric composition data for near-real-time monitoring and offline study, including retrievals of total column ozone (TCO) and an ultraviolet-absorbing aerosol index (AI) based on the version-8 total ozone (V8TOZ) algorithm. With the implementation of changes to employ a broadband channel approach in the NOAA OMPS V8TOZ, the retrieved TCO and AI products have become more stable and consistent between S-NPP and N20. Two particular regions have been chosen for building soft-calibration adjustments for both OMPS S-NPP and N20, which force the V8TOZ retrievals to be in quite good agreement from both sensors with little change by season. However, bias analysis shows that some noticeable errors and differences still exist after soft-calibration, and those errors appear to be quite persistently associated with solar zenith angle (SZA) and satellite viewing angle (SVA) in the retrievals of TCO and AI for both OMPS S-NPP and N20. Comparisons of TCO and AI from NOAA OMPS retrievals with other products such as those from the Tropospheric Monitoring Instrument (TROPOMI) and the Earth Polychromatic Imaging Camera (EPIC) show that, although the sensor, algorithm, and solar spectra are different among them, the overall retrievals from those products are quite similar and consistent. [ABSTRACT FROM AUTHOR]

We aim to evaluate the NO 2 absorption effect in aerosol columnar properties, namely the aerosol optical depth (AOD), Ångström exponent (AE), and single scattering albedo (SSA), derived from sun–sky radiometers in addition to the possible retrieval algorithm improvements by using more accurate characterization of NO 2 optical depth from co-located or satellite-based real-time measurements. For this purpose, we employ multiannual (2017–2022) records of AOD, AE, and SSA collected by sun photometers at an urban and a suburban site in the Rome area (Italy) in the framework of both the Aerosol Robotic Network (AERONET) and SKYNET networks. The uncertainties introduced in the aerosol retrievals by the NO 2 absorption are investigated using high-frequency observations of total NO 2 derived from co-located Pandora spectroradiometer systems in addition to spaceborne NO 2 products from the Tropospheric Monitoring Instrument (TROPOMI). For both AERONET and SKYNET, the standard network products were found to systematically overestimate AOD and AE. The average AOD bias found for Rome is relatively low for AERONET (∼ 0.002 at 440 nm and ∼ 0.003 at 380 nm) compared to the retrieval uncertainties but quite a bit higher for SKYNET (∼ 0.007). On average, an AE bias of ∼ 0.02 and ∼ 0.05 was estimated for AERONET and SKYNET, respectively. In general, the correction seems to be low for areas with low columnar NO 2 concentrations, but it is still useful for low AODs (< 0.3), where the majority of observations are found, especially under high NO 2 pollution events. For the cases of relatively high NO 2 levels (> 0.7 DU), the mean AOD bias was found within the range 0.009–0.012 for AERONET, depending on wavelength and location, and about 0.018 for SKYNET. The analysis does not reveal any significant impact of the NO 2 correction on the derived aerosol temporal trends for the very limited data sets used in this study. However, the effect is expected to become more evident for trends derived from larger data sets and in the case of an important NO 2 trend. In addition, the comparisons of the NO 2 -modified ground-based AOD data with satellite retrievals from the Deep Blue (DB) algorithm of the NASA Moderate Resolution Imaging Spectroradiometer (MODIS) resulted in a slight improvement in the agreement of about 0.003 and 0.006 for AERONET and SKYNET, respectively. Finally, the uncertainty in assumptions on NO 2 seems to have a non-negligible impact on the retrieved values of SSA at 440 nm leading to an average positive bias of about 0.02 (2 %) in both locations for high NO 2 loadings (> 0.7 DU). [ABSTRACT FROM AUTHOR]

The present study investigates the influences of stratospheric quasi-biennial oscillation (QBO) and El Niño–Southern Oscillation (ENSO) on the intensity of stratospheric isentropic mixing based on ERA-Interim and MERRA-2 reanalysis products. It is found that isentropic mixing in the stratosphere is modulated by QBO and ENSO. An analysis of the QBO basis function in the multiple regression model reveals that isentropic mixing in the lower stratosphere is suppressed in the equatorial region in the WQBO phase, while the mixing enhances in the subtropical and mid-latitude regions. This result is not consistent with the Holton–Tan mechanism. However, isentropic mixing in the mid-latitudes becomes stronger in the middle stratosphere in the EQBO phase, which agrees well with the Holton–Tan effect. Composite analysis indicates that QBO-induced changes in the direction and speed of the stratospheric zonal wind can affect wave propagation and wave breaking. In the WQBO phase, zonal wind weakens, and a planetary wave is anomalously converging near 30°N, which leads to an increase in isentropic mixing; on the contrary, wind speed becomes large, and the upward propagation of planetary wave divergence, which lead to the isentropic mixing, becomes weak near 60°N. In the EQBO phase, the wind is relatively weak around 60°N, and the isentropic mixing is strong. Multiple regression analysis reveals the ENSO impact on the intensity of isentropic mixing, which shows weak mixing in the middle and high latitudes and strong mixing in the low latitudes of the lower stratosphere in the El Niño years. In the middle stratosphere, isentropic mixing enhances in the mid-latitude region due to intensified upward propagation of planetary waves but weakens in the polar region. Composite analysis reveals a clear relationship between the mixing strength zones of the El Niño and La Niña years with the position of the polar jet and changes in zonal wind speed. [ABSTRACT FROM AUTHOR]

Bromine monoxide (BrO) is a key radical in the atmosphere, influencing the chemical state of the atmosphere, most notably the abundance of ozone. The main effect of BrO onto tropospheric ozone concentrations occurs in bromine release events in polar regions, salt pans and volcanic plumes. Ozone depletion caused by halogen release has been observed and modeled for such conditions, in particular inside volcanic plumes. Furthermore, the molar bromine to sulphur ratio in volcanic plumes is a proxy for the magmatic composition of a volcano and potentially an eruption forecast parameter. The integrated column of BrO in the atmosphere, which in turn serves as an estimate for the bromine content, can be detected simultaneously with SO2 via spectroscopic measurements using the Differential Optical Absorption Spectroscopy (DOAS). Thus, a direct derivation of the BrO/SO2 ratio can be performed from a single measurement. Satellite spectroscopic observations offer the potential to observe and monitor volcanic bromine release globally. The detection of BrO in volcanic plumes is limited by the precision and sensitivity of the retrieval, which so far only allowed for the detection of BrO during major eruptions, leading to a potential sampling bias when looking at the BrO/SO2 ratio. The The TROPospheric Monitoring Instrument (TROPOMI) onboard Sentinel-5 Precursor (S-5P) however, with its unprecedented spatial resolution of up to 3.5 × 5.5 km2 and high signal-to-noise ratio, enables the detection of BrO in minor eruptions or even quiescent degassing. In this study, we investigate, how far the BrO retrieval can be improved using TROPOMI data and how well BrO can be detected, even in small eruptions and during quiescent volcanic degassing. There are two steps, for which improvements in accuracy are investigated and applied: the improvement and quantitative determination of (1) the detection limit of the DOAS BrO column retrieval and (2) the correction of non-volcanic background BrO signal. First, the DOAS retrieval settings are varied and their influence on accuracy and precision is investigated with respect to the detection limit and potential systematic influences. Based on these results, we propose a dedicated DOAS evaluation scheme optimized for the detection of BrO in volcanic plumes. For the DOAS retrieval, we propose the use of a large fit window from 323–360 nm, yielding a factor of 1.8 lower statistical uncertainty compared to previous BrO DOAS algorithms, while not enhancing systematic influences. Second, the effect of the background BrO is reduced by a latitude dependent empirical correction scheme correlated to cloud information as well as information on the ozone column. Via these improvements, the combined statistical and systematic uncertainties of the resulting BrO vertical column density is in the order of 7 × 1012 molecules cm−2, which allows for the detection of even slightly enhanced BrO amounts inside minor eruptive plumes of bromine-rich volcanoes. [ABSTRACT FROM AUTHOR]

Ship-based multi-axis differential optical absorption spectroscopy (MAX-DOAS) measurements were conducted along the marginal seas of China from 19 April to 16 May 2018 to measure the vertical profiles of aerosol, nitrogen dioxide (NO 2), and nitrous acid (HONO). Along the cruise route, we found five hot spots with enhanced tropospheric NO 2 vertical column densities (VCDs) in the Yangtze River Delta, Taiwan Strait, Guangzhou–Hong Kong–Macau Greater Bay Area, port of Zhanjiang, and port of Qingdao. Enhanced HONO concentrations could usually be observed under high-level aerosol and NO 2 conditions, whereas the reverse was not always the case. To understand the impacts of relative humidity (RH), temperature, and aerosol on the heterogeneous reaction of NO 2 to form HONO in different scenarios, the Chinese Academy of Meteorological Sciences (CAMS) and Southern University of Science and Technology (SUST) MAX-DOAS stations were selected as the inland and coastal cases, respectively. The RH turning points in CAMS and SUST cases were both ∼ 65 % (60 %–70 %), whereas two turning peaks (∼ 60 % and ∼ 85 %) of RH were found in the sea cases. As temperature increased, the HONO / NO 2 ratio decreased with peak values appearing at ∼ 12.5 ∘ C in CAMS, whereas the HONO / NO 2 gradually increased and reached peak values at ∼ 31.5 ∘ C in SUST. In the sea cases, when the temperature exceeded 18.0 ∘ C, the HONO / NO 2 ratio rose with increasing temperature and achieved its peak at ∼ 25.0 ∘ C. This indicated that high temperature can contribute to the secondary formation of HONO in the sea atmosphere. In the inland cases, the correlation analysis between HONO and aerosol in the near-surface layer showed that the ground surface is more crucial to the formation of HONO via the heterogeneous reaction of NO 2 ; however, in the coastal and sea cases, the aerosol surface contributed more. Furthermore, we discovered that the conversion rate of NO 2 to HONO through heterogeneous reactions in the sea cases is larger than that in the inland cases in higher atmospheric layers (> 600 m). Three typical events were selected to demonstrate three potential contributing factors of HONO production under marine conditions (i.e., transport, NO 2 heterogeneous reaction, and unknown HONO source). This study elucidates the sea–land and vertical differences in the forming mechanism of HONO via the NO 2 heterogeneous reaction and provides deep insights into tropospheric HONO distribution, transforming process, and environmental effects. [ABSTRACT FROM AUTHOR]

Nitrogen oxides, collectively referred to as NO x (NO + NO 2), are an important component of atmospheric chemistry involved in the production and destruction of various oxidants that contribute to the oxidative capacity of the troposphere. The primary sink for NO x is atmospheric nitrate, which has an influence on climate and the biogeochemical cycling of reactive nitrogen. NO x sources and NO x -to-NO 3- formation pathways remain poorly constrained in the remote marine boundary layer of the Southern Ocean, particularly outside of the more frequently sampled summer months. This study presents seasonally resolved measurements of the isotopic composition (δ15 N, δ18 O, and Δ17 O) of atmospheric nitrate in coarse-mode (> 1 µ m) aerosols, collected between South Africa and the sea ice edge in summer, winter, and spring. Similar latitudinal trends in δ15 N–NO 3- were observed in summer and spring, suggesting similar NO x sources. Based on δ15 N–NO 3- , the main NO x sources were likely a combination of lightning, biomass burning, and/or soil emissions at the low latitudes, as well as oceanic alkyl nitrates and snowpack emissions from continental Antarctica or the sea ice at the mid-latitudes and high latitudes, respectively. Snowpack emissions associated with photolysis were derived from both the Antarctic snowpack and snow on sea ice. A combination of natural NO x sources, likely transported from the lower-latitude Atlantic, contribute to the background-level NO 3- observed in winter, with the potential for a stratospheric NO 3- source evidenced by one sample of Antarctic origin. Greater values of δ18 O–NO 3- in spring and winter compared to summer suggest an increased influence of oxidation pathways that incorporate oxygen atoms from O 3 into the end product NO 3- (i.e. N 2 O 5 , DMS, and halogen oxides (XO)). Significant linear relationships between δ18 O and Δ17 O suggest isotopic mixing between H 2 O (v) and O 3 in winter and isotopic mixing between H 2 O (v) and O 3 /XO in spring. The onset of sunlight in spring, coupled with large sea ice extent, can activate chlorine chemistry with the potential to increase peroxy radical concentrations, contributing to oxidant chemistry in the marine boundary layer. As a result, isotopic mixing with an additional third end-member (atmospheric O 2) occurs in spring. [ABSTRACT FROM AUTHOR]

Few studies have investigated the impact of new particle formation (NPF) on cloud condensation nuclei (CCN) in remote Antarctica, and none has elucidated the relationship between NPF and CCN production. To address that knowledge gap, we continuously measured the number size distribution of 2.5–300 nm particles and CCN number concentrations at King Sejong Station in the Antarctic Peninsula from January 1 to December 31, 2018. Ninety-seven new particle formation (NPF) events were detected throughout the year. The estimated median spatial scale of NPF around Antarctic peninsula was found to be approximately 155 km, indicating the large-scale of NPF events. Air back-trajectory analysis revealed that 80 cases of NPF events were associated with air masses originating over the ocean, followed by sea ice (12 cases), multiple (3 cases), and land (2 cases) regions. We present and discuss three major NPF categories: (1) marine NPF (2) sea ice NPF, and (3) multiple NPF. Our results showed that the photo-oxidation of oceanic biogenic precursors such as dimethyl sulfide (DMS) could be a key component in marine NPF events, whereas halogen compounds released from ice-covered areas could contribute to sea-ice NPF events. Terrestrial sources (wild life colonies, vegetation, and meltwater ponds) from Antarctica could affect aerosol production in multiple air masses. Out of 97 observed NPF events, 83 cases were characterized by the simultaneous increase in the CCN concentration by 2–270 % (median 44 %) in the following 1 to 36 hours (median 8 hours) after NPF events. Overall, Antarctic NPF events were found to be a significant source of particles with different physical characteristics and related to biogenic sources in and around the Antarctic Peninsula, which subsequently grew to cloud nuclei. [ABSTRACT FROM AUTHOR]

The global methane pledge paves a fresh, critical way toward carbon neutrality. However, it remains largely invisible and highly controversial due to the fact that planet-scale and plant-level methane retrievals have rarely been coordinated. This has never been more essential within the narrow window to reach the Paris target. Here we present a two-tiered spaceborne architecture to address this issue. Using this framework, we focused on the United States, China, the Middle East, and North Africa, and simultaneously uncovered methane-abundant regions and plumes. These include new super-emitters, potential leakages, and unprecedented multiple plumes in a single source. More importantly, this framework is shown to challenge official emission reports that possibly mislead estimates from global, regional, and site scales, particularly by missing super-emitters. Our results show that, in principle, the above framework can be extended to be multi-tiered by adding upcoming stereoscopic measurements and suitable artificial intelligence, and thus it is sufficiently versatile for immediate and future monitoring of the global methane pledge. [ABSTRACT FROM AUTHOR]

Satellite retrievals of tropospheric-column formaldehyde (HCHO) and nitrogen dioxide (NO 2) are frequently used to investigate the sensitivity of ozone (O 3) production to emissions of nitrogen oxides and volatile organic carbon compounds. This study inter-compared the systematic biases and uncertainties in retrievals of NO 2 and HCHO, as well as resulting HCHO–NO 2 ratios (FNRs), from two commonly applied satellite sensors to investigate O 3 production sensitivities (Ozone Monitoring Instrument, OMI, and TROPOspheric Monitoring Instrument, TROPOMI) using airborne remote-sensing data taken during the Long Island Sound Tropospheric Ozone Study 2018 between 25 June and 6 September 2018. Compared to aircraft-based HCHO and NO 2 observations, the accuracy of OMI and TROPOMI were magnitude-dependent with high biases in clean environments and a tendency towards more accurate comparisons to even low biases in moderately polluted to polluted regions. OMI and TROPOMI NO 2 systematic biases were similar in magnitude (normalized median bias, NMB = 5 %–6 %; linear regression slope ≈ 0.5–0.6), with OMI having a high median bias and TROPOMI resulting in small low biases. Campaign-averaged uncertainties in the three satellite retrievals (NASA OMI; Quality Assurance for Essential Climate Variables, QA4ECV OMI; and TROPOMI) of NO 2 were generally similar, with TROPOMI retrievals having slightly less spread in the data compared to OMI. The three satellite products differed more when evaluating HCHO retrievals. Campaign-averaged tropospheric HCHO retrievals all had linear regression slopes ∼0.5 and NMBs of 39 %, 17 %, 13 %, and 23 % for NASA OMI, QA4ECV OMI, and TROPOMI at finer (0.05∘×0.05∘) and coarser (0.15∘×0.15∘) spatial resolution, respectively. Campaign-averaged uncertainty values (root mean square error, RMSE) in NASA and QA4ECV OMI HCHO retrievals were ∼9.0×1015 molecules cm -2 (∼ 50 %–55 % of mean column abundance), and the higher-spatial-resolution retrievals from TROPOMI resulted in RMSE values ∼30 % lower. Spatially averaging TROPOMI tropospheric-column HCHO, along with NO 2 and FNRs, to resolutions similar to the OMI reduced the uncertainty in these retrievals. Systematic biases in OMI and TROPOMI NO 2 and HCHO retrievals tended to cancel out, resulting in all three satellite products comparing well to observed FNRs. However, while satellite-derived FNRs had minimal campaign-averaged median biases, unresolved errors in the indicator species did not cancel out in FNR calculations, resulting in large RMSE values compared to observations. Uncertainties in HCHO retrievals were determined to drive the unresolved biases in FNR retrievals. [ABSTRACT FROM AUTHOR]

The paper presents an innovative approach in the modelling of multi-storey timber-framed buildings, where double-skin façade elements (DSF) are additionally considered as load-bearing wall elements against a horizontal load impact. The mathematical model with a fictive diagonal element developed for timber-framed wall elements with classical oriented strand boards (OSB) or fibre–plaster sheathing boards (FPB) is upgraded for DSF elements. The diameter of the fictive diagonal is determined with either experimental results or numerically obtained results using the time-consuming FEM model with elastic spring elements, which simulates the bonding line between the timber frame and both glazing panes. In the second part of the study, the numerical analysis of a specially selected three-storey timber-framed building was performed using the developed mathematical model with fictive diagonal elements. Two alternative calculations were performed with the DSF elements as non-resisting and racking-resisting wall elements. It was demonstrated on the selected case that the racking resistance (R) of a building can essentially increase up to 35% if DSF elements are considered as resisting wall elements. As a secondary goal of the study, it is also important to point out that by using DSF elements as racking-resisting elements, the distortion in the first floor essentially decreased. It is demonstrated on the selected numerical example that this torsional influence decreased notably (by almost 18%) when the load-bearing DSF elements were used for seismic excitation in the X direction. Therefore, such an approach can open new perspectives in designing multi-storey timber-framed buildings with a more attractive and dynamic floor plan and structure. [ABSTRACT FROM AUTHOR]

In orbit since late 2017, the Tropospheric Monitoring Instrument (TROPOMI) is offering new outstanding opportunities for better understanding the emission and fate of nitrogen dioxide (NO 2) pollution in the troposphere. In this study, we provide a comprehensive analysis of the spatio-temporal variability of TROPOMI NO 2 tropospheric columns (TrC-NO 2) over the Iberian Peninsula during 2018–2021, considering the recently developed Product Algorithm Laboratory (PAL) product. We complement our analysis with estimates of NO x anthropogenic and natural soil emissions. Closely related to cloud cover, the data availability of TROPOMI observations ranges from 30 %–45 % during April and November to 70 %–80 % during summertime, with strong variations between northern and southern Spain. Strongest TrC-NO 2 hotspots are located over Madrid and Barcelona, while TrC-NO 2 enhancements are also observed along international maritime routes close the strait of Gibraltar, and to a lesser extent along specific major highways. TROPOMI TrC-NO 2 appear reasonably well correlated with collocated surface NO 2 mixing ratios, with correlations around 0.7–0.8 depending on the averaging time. We investigate the changes of weekly and monthly variability of TROPOMI TrC-NO 2 depending on the urban cover fraction. Weekly profiles show a reduction of TrC-NO 2 during the weekend ranging from - 10 % to - 40 % from least to most urbanized areas, in reasonable agreement with surface NO 2. In the largest agglomerations like Madrid or Barcelona, this weekend effect peaks not in the city center but in specific suburban areas/cities, suggesting a larger relative contribution of commuting to total NO x anthropogenic emissions. The TROPOMI TrC-NO 2 monthly variability also strongly varies with the level of urbanization, with monthly differences relative to annual mean ranging from - 40 % in summer to + 60 % in winter in the most urbanized areas, and from - 10 % to + 20 % in the least urbanized areas. When focusing on agricultural areas, TROPOMI observations depict an enhancement in June–July that could come from natural soil NO emissions. Some specific analysis of surface NO 2 observations in Madrid show that the relatively sharp NO 2 minimum used to occur in August (drop of road transport during holidays) has now evolved into a much broader minimum partly de-coupled from the observed local road traffic counting; this change started in 2018, thus before the COVID-19 outbreak. Over 2019–2021, a reasonable consistency of the inter-annual variability of NO 2 is also found between both datasets. Our study illustrates the strong potential of TROPOMI TrC-NO 2 observations for complementing the existing surface NO 2 monitoring stations, especially in the poorly covered rural and maritime areas where NO x can play a key role, notably for the production of tropospheric O 3. [ABSTRACT FROM AUTHOR]

We introduce the new Global Ozone Monitoring Experiment-2 (GOME-2) daily and monthly level-3 product of total column ozone (O 3), total and tropospheric column nitrogen dioxide (NO 2), total column water vapour, total column bromine oxide (BrO), total column formaldehyde (HCHO), and total column sulfur dioxide (SO 2) (daily products 10.15770/EUM_SAF_AC_0048, ; monthly products 10.15770/EUM_SAF_AC_0049,). The GOME-2 level-3 products aim to provide easily translatable and user-friendly data sets to the scientific community for scientific progress as well as to satisfy public interest. The purpose of this paper is to present the theoretical basis as well as the verification and validation of the GOME-2 daily and monthly level-3 products. The GOME-2 level-3 products are produced using the overlapping area-weighting method. Details of the gridding algorithm are presented. The spatial resolution of the GOME-2 level-3 products is selected based on the sensitivity study. The consistency of the resulting level-3 products among three GOME-2 sensors is investigated through time series of global averages, zonal averages, and bias. The accuracy of the products is validated by comparison to ground-based observations. The verification and validation results show that the GOME-2 level-3 products are consistent with the level-2 data. Small discrepancies are found among three GOME-2 sensors, which are mainly caused by the differences in the instrument characteristic and level-2 processor. The comparison of GOME-2 level-3 products to ground-based observations in general shows very good agreement, indicating that the products are consistent and fulfil the requirements to serve the scientific community and general public. [ABSTRACT FROM AUTHOR]

The remoteness and extreme conditions of the Southern Ocean and Antarctic region have meant that observations in this region are rare, and typically restricted to summertime during research or resupply voyages. Observations of aerosols outside of the summer season are typically limited to long-term stations, such as Kennaook / Cape Grim (KCG; 40.7 ∘ S, 144.7 ∘ E), which is situated in the northern latitudes of the Southern Ocean, and Antarctic research stations, such as the Japanese operated Syowa (SYO; 69.0 ∘ S, 39.6 ∘ E). Measurements in the midlatitudes of the Southern Ocean are important, particularly in light of recent observations that highlighted the latitudinal gradient that exists across the region in summertime. Here we present 2 years (March 2016–March 2018) of observations from Macquarie Island (MQI; 54.5 ∘ S, 159.0 ∘ E) of aerosol (condensation nuclei larger than 10 nm, CN 10) and cloud condensation nuclei (CCN at various supersaturations) concentrations. This important multi-year data set is characterised, and its features are compared with the long-term data sets from KCG and SYO together with those from recent, regionally relevant voyages. CN 10 concentrations were the highest at KCG by a factor of ∼50% across all non-winter seasons compared to the other two stations, which were similar (summer medians of 530, 426 and 468 cm-3 at KCG, MQI and SYO, respectively). In wintertime, seasonal minima at KCG and MQI were similar (142 and 152 cm-3 , respectively), with SYO being distinctly lower (87 cm-3), likely the result of the reduction in sea spray aerosol generation due to the sea ice ocean cover around the site. CN 10 seasonal maxima were observed at the stations at different times of year, with KCG and MQI exhibiting January maxima and SYO having a distinct February high. Comparison of CCN 0.5 data between KCG and MQI showed similar overall trends with summertime maxima and wintertime minima; however, KCG exhibited slightly (∼10%) higher concentrations in summer (medians of 158 and 145 cm-3 , respectively), whereas KCG showed ∼40% lower concentrations than MQI in winter (medians of 57 and 92 cm-3 , respectively). Spatial and temporal trends in the data were analysed further by contrasting data to coincident observations that occurred aboard several voyages of the RSV Aurora Australis and the RV Investigator. Results from this study are important for validating and improving our models and highlight the heterogeneity of this pristine region and the need for further long-term observations that capture the seasonal cycles. [ABSTRACT FROM AUTHOR]

The tropospheric concentrations of nitrogen dioxide (NO 2) and formaldehyde (HCHO) have high spatio-temporal variability, and in situ observations of these trace gases are still scarce, especially in remote background areas. We made four similar circling journeys of mobile multi-axis differential optical absorption spectroscopy (MAX-DOAS) measurements in the Three Rivers' Source region over the Tibetan Plateau in summer (18–30 July) 2021 for the first time. The differential slant column densities (DSCDs) of NO 2 and HCHO were retrieved from the measured spectra, with very weak absorptions along the driving routes. The tropospheric NO 2 and HCHO vertical column densities (VCDs) were calculated from their DSCDs by the geometric approximation method, and they were further filtered to form reliable data sets by eliminating the influences of sunlight shelters and the vehicle's vibration and bumpiness. The observational data show that the tropospheric NO 2 and HCHO VCDs decreased with the increasing altitude of the driving route, whose background levels ± standard deviations were 0.40 ± 1.13×1015 molec. cm -2 for NO 2 and 2.27±1.66×1015 molec. cm -2 for HCHO in July 2021 over the Three Rivers' Source region. The NO 2 VCDs show similar geographical distribution patterns between the different circling journeys, but the levels of the HCHO VCDs are different between the different circling journeys. The elevated NO 2 VCDs along the driving routes usually corresponded to enhanced transport emissions from the towns crossed. However, the spatial distributions of the HCHO VCDs depended significantly on natural and meteorological conditions, such as surface temperature. By comparing TROPOMI satellite products and mobile MAX-DOAS results, we found that TROPOMI NO 2 and HCHO VCDs have large positive offsets in the background atmosphere over the main area of the Three Rivers' Source. Our study provides valuable data sets and information of NO 2 and HCHO over the Tibetan Plateau, benefitting the scientific community in investigating the spatio-temporal evolution of atmospheric composition in the background atmosphere at high altitudes, validating and improving the satellite products over mountain terrains, and evaluating the model's ability to simulate atmospheric chemistry over the Tibetan Plateau. [ABSTRACT FROM AUTHOR]

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

The presence of reactive bromine in polar regions is a widespread phenomenon that plays an important role in the photochemistry of the Arctic and Antarctic lower troposphere, including the destruction of ozone, the disturbance of radical cycles, and the oxidation of gaseous elemental mercury. The chemical mechanisms leading to the heterogeneous release of gaseous bromine compounds from saline surfaces are in principle well understood. There are, however, substantial uncertainties about the contribution of different potential sources to the release of reactive bromine, such as sea ice, brine, aerosols, and the snow surface, as well as about the seasonal and diurnal variation and the vertical distribution of reactive bromine. Here we use continuous long-term measurements of the vertical distribution of bromine monoxide (BrO) and aerosols at the two Antarctic sites Neumayer (NM) and Arrival Heights (AH), covering the periods of 2003–2021 and 2012–2021, respectively, to investigate how chemical and physical parameters affect the abundance of BrO. We find the strongest correlation between BrO and aerosol extinction (R=0.56 for NM and R=0.28 for AH during spring), suggesting that the heterogeneous release of Br2 from saline airborne particles (blowing snow and aerosols) is a dominant source for reactive bromine. Positive correlations between BrO and contact time of air masses, both with sea ice and the Antarctic ice sheet, suggest that reactive bromine is not only emitted by the sea ice surface but by the snowpack on the ice shelf and in the coastal regions of Antarctica. In addition, the open ocean appears to represent a source for reactive bromine during late summer and autumn when the sea ice extent is at its minimum. A source–receptor analysis based on back trajectories and sea ice maps shows that main source regions for BrO at NM are the Weddell Sea and the Filchner–Ronne Ice Shelf, as well as coastal polynyas where sea ice is newly formed. A strong morning peak in BrO frequently occurring during summer and that is particularly strong during autumn suggests a night-time build-up of Br2 by heterogeneous reaction of ozone on the saline snowpack in the vicinity of the measurement sites. We furthermore show that BrO can be sustained for at least 3 d while travelling across the Antarctic continent in the absence of any saline surfaces that could serve as a source for reactive bromine. [ABSTRACT FROM AUTHOR]

Airborne imaging differential optical absorption spectroscopy (DOAS), ground-based stationary DOAS, and car DOAS measurements were conducted during the S5P-VAL-DE-Ruhr campaign in September 2020. The campaign area is located in the Rhine-Ruhr region of North Rhine-Westphalia, western Germany, which is a pollution hotspot in Europe comprising urban and large industrial sources. The DOAS measurements are used to validate spaceborne NO 2 tropospheric vertical column density (VCD) data products from the Sentinel-5 Precursor (S5P) TROPOspheric Monitoring Instrument (TROPOMI). Seven flights were performed with the airborne imaging DOAS instrument for measurements of atmospheric pollution (AirMAP), providing measurements that were used to create continuous maps of NO 2 in the layer below the aircraft. These flights cover many S5P ground pixels within an area of 30 km × 35 km and were accompanied by ground-based stationary measurements and three mobile car DOAS instruments. Stationary measurements were conducted by two Pandora, two Zenith-DOAS, and two MAX-DOAS instruments. Ground-based stationary and car DOAS measurements are used to evaluate the AirMAP tropospheric NO 2 VCDs and show high Pearson correlation coefficients of 0.88 and 0.89 and slopes of 0.90 ± 0.09 and 0.89 ± 0.02 for the stationary and car DOAS, respectively. Having a spatial resolution of about 100 m × 30 m, the AirMAP tropospheric NO 2 VCD data create a link between the ground-based and the TROPOMI measurements with a nadir resolution of 3.5 km × 5.5 km and are therefore well suited to validate the TROPOMI tropospheric NO 2 VCD. The observations on the 7 flight days show strong NO 2 variability, which is dependent on the three target areas, the day of the week, and the meteorological conditions. The AirMAP campaign data set is compared to the TROPOMI NO 2 operational offline (OFFL) V01.03.02 data product, the reprocessed NO 2 data using the V02.03.01 of the official level-2 processor provided by the Product Algorithm Laboratory (PAL), and several scientific TROPOMI NO 2 data products. The AirMAP and TROPOMI OFFL V01.03.02 data are highly correlated (r=0.87) but show an underestimation of the TROPOMI data with a slope of 0.38 ± 0.02 and a median relative difference of - 9 %. With the modifications in the NO 2 retrieval implemented in the PAL V02.03.01 product, the slope and median relative difference increased to 0.83 ± 0.06 and + 20 %. However, the modifications resulted in larger scatter and the correlation decreased significantly to r=0.72. The results can be improved by not applying a cloud correction for the TROPOMI data in conditions with high aerosol load and when cloud pressures are retrieved close to the surface. The influence of spatially more highly resolved a priori NO 2 vertical profiles and surface reflectivity are investigated using scientific TROPOMI tropospheric NO 2 VCD data products. The comparison of the AirMAP campaign data set to the scientific data products shows that the choice of surface reflectivity database has a minor impact on the tropospheric NO 2 VCD retrieval in the campaign region and season. In comparison, the replacement of the a priori NO 2 profile in combination with the improvements in the retrieval of the PAL V02.03.01 product regarding cloud heights can further increase the tropospheric NO 2 VCDs. This study demonstrates that the underestimation of the TROPOMI tropospheric NO 2 VCD product with respect to the validation data set has been and can be further significantly improved. [ABSTRACT FROM AUTHOR]

The Satellite Coastal and Oceanic Atmospheric Pollution Experiment (SCOAPE) cruise in the Gulf of Mexico was conducted in May 2019 by NASA and the Bureau of Ocean Energy Management to determine the feasibility of using satellite data to measure air quality in a region of concentrated oil and natural gas (ONG) operations. SCOAPE addressed both technological and scientific issues related to measuring NO2 columns over the outer continental shelf. Featured were nitrogen dioxide (NO2) instruments (Pandora, Teledyne API analyzer) at Cocodrie, LA (29.26°, −90.66°), and on the Research Vessel Point Sur operating off the Louisiana coast with measurements of ozone, carbon monoxide, and volatile organic compounds (VOCs). The findings: (a) all NO2 observations revealed two atmospheric regimes over the Gulf, the first influenced by tropical air in 10–14 May, the second influenced by flow from urban areas on 15–17 May; (b) comparisons of OMI v4 and TROPOMI v1.3 TC (total column) NO2 data with shipboard Pandora NO2 column observations averaged 13% agreement with the largest difference during 15–17 May (∼20%). At Cocodrie, the satellite–Pandora agreement was ∼5%. (c) Three new‐model Pandora instruments displayed a TC NO2 precision of 0.01 Dobson Units (∼5%); (d) regions of smaller, older natural gas operations showed high methane readings from leakage; elevated VOCs were also detected. Neither satellite nor spectrometer captured the magnitude of ambient NO2 variability near ONG platforms. Given an absence of regular air quality monitoring over the Gulf of Mexico, SCOAPE data constitute a baseline against which future observations can be compared. Plain Language Summary: The Satellite Coastal and Oceanic Atmospheric Pollution Experiment (SCOAPE) cruise in the Gulf of Mexico (GOM) conducted on the Research Vessel Point Sur in May 2019 investigated the feasibility of using satellite data to measure air quality in a region of concentrated oil and natural gas (ONG) operations. SCOAPE addressed both technological and scientific issues related to measuring NO2 columns in a prototypical coastal environment. The results are as follows. First, measurements from SCOAPE demonstrated that satellite NO2 data can be used to monitor ONG activity over the GOM. Second, during SCOAPE both OMI and TROPOMI TC (total column) NO2 amounts were higher over land and sometimes the near‐shore ONG‐rich Gulf, than over deepwater regions farther offshore. This was confirmed by Pandora spectrometer "ground truth" TC NO2 data measured throughout SCOAPE on shore and on ship. Third, SCOAPE established the reliability and precision of a new generation of Pandora spectrometers. Fourth, comparisons of satellite and Pandora TC NO2 data in SCOAPE confirm previous land–water interface studies that point to limitations in satellite NO2 in coastal regions. Finally, neither satellite nor spectrometer captures the magnitude of ambient ("nose‐level") NO2 variability in a region dotted with hundreds of ONG platforms. Key Points: Shipboard Pandora NO2 columns and surface O3, NO2, CO, and volatile organic compounds (VOCs) over the Gulf of Mexico (GOM), May 2019, displayed two air quality (AQ) regimesGOM AQ was dominated by continental NO2 sources and near‐shore VOC; deepwater oil platforms were in a clean marine regimePandora and satellite total column NO2 over GOM agreed overall within 5% in clean, clear‐sky conditions along the coast and 13% over water [ABSTRACT FROM AUTHOR]

In this article, we investigate the spatio-temporal variability of tropospheric NO2 Vertical Column Densities (VCDs) and surface concentrations that were retrieved using Multi-Axis Differential Optical Absorption Spectroscopy (MAX-DOAS) measurements over Thessaloniki, Greece, for the period June 2020 to November 2022. The MAX-DOAS system captures the NO2 seasonal variability very well, reporting low concentrations during summer and higher concentrations in the winter, as well as the diurnal cycle with higher NO2 amounts in the morning followed by a reduction towards noon. The "weekend effect" is evident, with approximately 30% lower NO2 concentrations on the weekends compared to the working days. An excellent agreement is found with in situ data from a nearby air quality monitoring station with Pearson's correlation coefficients ranging between R = 0.90 and R = 0.99. The spatial variability is assessed by comparing the NO2 concentrations at four azimuth viewing directions of the MAX-DOAS system. Despite the large variability due to short- and long-term temporal variations, higher NO2 concentrations of up to 25% (statistically significant at the 95% confidence level) are reported for the azimuth that crosses the entire city center and an urban area compared to those pointing towards the sea. The MAX-DOAS tropospheric NO2 columns are then compared to those measured by the TROPOspheric Monitoring Instrument (TROPOMI) on board the Sentinel-5P satellite. Despite the generally good correlation (R = 0.72 and R = 0.89 for the daily and monthly data, respectively), a clear underestimation of TROPOMI is found (approximately 55% in winter, 21% in spring and 40% during autumn and summer), mainly due to the much larger satellite footprint that provides a smoother perception of the NO2 concentration, while the MAX-DOAS measurements are more affected by local emissions. [ABSTRACT FROM AUTHOR]

The availability of formaldehyde (HCHO) (a proxy for volatile organic compound reactivity) and nitrogen dioxide (NO 2) (a proxy for nitrogen oxides) tropospheric columns from ultraviolet–visible (UV–Vis) satellites has motivated many to use their ratios to gain some insights into the near-surface ozone sensitivity. Strong emphasis has been placed on the challenges that come with transforming what is being observed in the tropospheric column to what is actually in the planetary boundary layer (PBL) and near the surface; however, little attention has been paid to other sources of error such as chemistry, spatial representation, and retrieval uncertainties. Here we leverage a wide spectrum of tools and data to quantify those errors carefully. Concerning the chemistry error, a well-characterized box model constrained by more than 500 h of aircraft data from NASA's air quality campaigns is used to simulate the ratio of the chemical loss of HO 2 + RO 2 (LROx) to the chemical loss of NO x (LNOx). Subsequently, we challenge the predictive power of HCHO/NO2 ratios (FNRs), which are commonly applied in current research, in detecting the underlying ozone regimes by comparing them to LROx/LNOx. FNRs show a strongly linear (R2=0.94) relationship with LROx/LNOx , but only on the logarithmic scale. Following the baseline (i.e., ln(LROx/LNOx) = - 1.0 ± 0.2) with the model and mechanism (CB06, r2) used for segregating NOx -sensitive from VOC-sensitive regimes, we observe a broad range of FNR thresholds ranging from 1 to 4. The transitioning ratios strictly follow a Gaussian distribution with a mean and standard deviation of 1.8 and 0.4, respectively. This implies that the FNR has an inherent 20 % standard error (1σ) resulting from not accurately describing the ROx – HOx cycle. We calculate high ozone production rates (PO 3) dominated by large HCHO × NO 2 concentration levels, a new proxy for the abundance of ozone precursors. The relationship between PO 3 and HCHO × NO 2 becomes more pronounced when moving towards NOx -sensitive regions due to nonlinear chemistry; our results indicate that there is fruitful information in the HCHO × NO 2 metric that has not been utilized in ozone studies. The vast amount of vertical information on HCHO and NO 2 concentrations from the air quality campaigns enables us to parameterize the vertical shapes of FNRs using a second-order rational function permitting an analytical solution for an altitude adjustment factor to partition the tropospheric columns into the PBL region. We propose a mathematical solution to the spatial representation error based on modeling isotropic semivariograms. Based on summertime-averaged data, the Ozone Monitoring Instrument (OMI) loses 12 % of its spatial information at its native resolution with respect to a high-resolution sensor like the TROPOspheric Monitoring Instrument (TROPOMI) (> 5.5 × 3.5 km 2). A pixel with a grid size of 216 km 2 fails at capturing ∼ 65 % of the spatial information in FNRs at a 50 km length scale comparable to the size of a large urban center (e.g., Los Angeles). We ultimately leverage a large suite of in situ and ground-based remote sensing measurements to draw the error distributions of daily TROPOMI and OMI tropospheric NO 2 and HCHO columns. At a 68 % confidence interval (1σ), errors pertaining to daily TROPOMI observations, either HCHO or tropospheric NO 2 columns, should be above 1.2–1.5 × 10 16 molec. cm -2 to attain a 20 %–30 % standard error in the ratio. This level of error is almost non-achievable with the OMI given its large error in HCHO. The satellite column retrieval error is the largest contributor to the total error (40 %–90 %) in the FNRs. Due to a stronger signal in cities, the total relative error (< 50 %) tends to be mild, whereas areas with low vegetation and anthropogenic sources (e.g., the Rocky Mountains) are markedly uncertain (> 100 %). Our study suggests that continuing development in the retrieval algorithm and sensor design and calibration is essential to be able to advance the application of FNRs beyond a qualitative metric. [ABSTRACT FROM AUTHOR]

In this study, a green chemistry method was used to synthesize polymer composites based on polyethylene oxide (PEO). The method of the remediation of metal complexes used in this study is an environmentally friendly procedure with a low cost. Zinc metal ion (Zn2+)-polyphenol (PPHNL) complexes were synthesized for two minutes via the combination of a black tea leaf (BTL) extract solution with dissolved Zn-acetate. Then, UV–Vis and FTIR were carried out for the Zn-PPHNL complexes in a liquid and solid. The FTIR spectra show that BTLs contain sufficient functional groups (O-H, C-H, C=O, C=C, C-O, C-N, and N-H), PPHNL, and conjugated double bonds to produce metal complexes by capturing the cations of Zn-acetate salt. Moreover, FTIR of the BTL and Zn–PPHNL complexes approves the formation of the Zn-PPHNL complex over the wide variation in the intensity of bands. The UV absorption spectra of BTL and Zn-PPHNL indicate complex formation among tea PPHNL and Zn cations, which enhances the absorption spectra of the Zn-PPHNL to 0.1 compared to the figure of 0.01 associated with the extracted tea solution. According to an XRD analysis, an amorphous Zn-PPHNL complex was created when Zn2+ ions and PPHNL interacted. Additionally, XRD shows that the structure of the PEO composite becomes a more amorphous structure as the concentration of Zn-PPHNL increases. Furthermore, morphological study via an optical microscope (OM) shows that by increasing the concentration of Zn-PPHNL in a PEO polymer composite the size of the spherulites ascribed to the crystalline phase dramatically decreases. The optical properties of PEO: Zn-PPHNL films, via UV–Vis spectroscopy, were rigorously studied. The Eg is calculated by examining the dielectric loss, which is reduced from 5.5 eV to 0.6 eV by increasing the concentration of Zn-PPHNL in the PEO samples. In addition, Tauc's form was used to specify the category of electronic transitions in the PEO: Zn-PPHNL films. The impact of crystalline structure and morphology on electronic transition types was discussed. Macroscopic measurable parameters, such as the refractive index and extinction coefficient, were used to determine optical dielectric loss. Fundamental optical dielectric functions were used to determine some key parameters. From the viewpoint of quantum transport, electron transitions were discussed. The merit of this work is that microscopic processes related to electron transition from the VB to the CB can be interpreted interms of measurable macroscopic quantities. [ABSTRACT FROM AUTHOR]

We report on airborne limb and nadir measurements of vertical profiles and total vertical column densities (VCDs) of glyoxal (C2H2O2) in the troposphere, which were performed aboard the German research aircraft HALO (High Altitude and LOng Range) in different regions and seasons around the globe between 2014 and 2019. The airborne nadir and integrated limb profiles agree excellently among each other. Our airborne observations are further compared to collocated glyoxal measurements of the TROPOspheric Monitoring Instrument (TROPOMI), with good agreement between both data sets for glyoxal observations in (1) pristine terrestrial, (2) pristine marine, (3) mixed polluted, and (4) biomass-burning-affected air masses with high glyoxal concentrations. Exceptions to the overall good agreement are observations of (1) faint and aged biomass burning plumes over the oceans and (2) of low-lying biomass burning or anthropogenic plumes in the terrestrial or marine boundary layer, both of which contain elevated glyoxal that is mostly not captured by TROPOMI. These differences in airborne and satellite-detected glyoxal are most likely caused by the overall small contribution of plumes of a limited extent to the total glyoxal absorption in the atmosphere and the difficulty in remotely detecting weak absorbers located close to low reflective surfaces (e.g. the ocean in the visible wavelength range) or within dense aerosol layers. Observations of glyoxal in aged biomass burning plumes (e.g. observed over the tropical Atlantic off the coast of West Africa in summer 2018, off the coast of Brazil by the end of the dry season 2019, and the East China Sea in spring 2018) could be traced back to related wildfires, such as a plume crossing over the Drake Passage that originated from the Australian bushfires in late 2019. Our observations of glyoxal in such aged biomass burning plumes confirm recent findings of enhanced glyoxal and presumably secondary organic aerosol (SOA) formation in aged wildfire plumes from yet-to-be-identified, longer-lived organic precursor molecules (e.g. aromatics, acetylene, or aliphatic compounds) co-emitted in the fires. Furthermore, elevated glyoxal (median 44 ppt – parts per trillion), as compared to other marine regions (median 10–19 ppt), is observed in the boundary layer over the tropical oceans, which is well in agreement with previous reports. The airborne data sets are further compared to glyoxal simulations performed with the global atmosphere chemistry model EMAC (ECHAM/MESSy Atmospheric Chemistry). When using an EMAC set up that resembles recent EMAC studies focusing on complex chemistry, reasonable agreement is found for pristine air masses (e.g. the unperturbed free and upper troposphere), but a notable glyoxal overestimation of the model exists for regions with high emissions of glyoxal and glyoxal-producing volatile organic compounds (VOCs) from the biosphere (e.g. the Amazon). In all other investigated regions, the model underpredicts glyoxal to varying degrees, in particular when probing mixed emissions from anthropogenic activities (e.g. over continental Europe, the Mediterranean, and East China Sea) and potentially from the sea (e.g. the tropical oceans). Also, the model tends to largely underpredict glyoxal in city plumes and aged biomass burning plumes. The potential causes for these differences are likely to be multifaceted, but they all point to missing glyoxal sources from the degradation of the mixture of potentially longer-chained organic compounds emitted from anthropogenic activities, biomass burning, and from the organic microlayer of the sea surface. [ABSTRACT FROM AUTHOR]

The atmospheric boundary layer (ABL) defines the volume of air adjacent to the Earth's surface for the dilution of heat, moisture, and trace substances. Quantitative knowledge on the temporal and spatial variations in the heights of the ABL and its sub-layers is still scarce, despite their importance for a series of applications (including, for example, air quality, numerical weather prediction, greenhouse gas assessment, and renewable energy production). Thanks to recent advances in ground-based remote-sensing measurement technology and algorithm development, continuous profiling of the entire ABL vertical extent at high temporal and vertical resolution is increasingly possible. Dense measurement networks of autonomous ground-based remote-sensing instruments, such as microwave radiometers, radar wind profilers, Doppler wind lidars or automatic lidars and ceilometers are hence emerging across Europe and other parts of the world. This review summarises the capabilities and limitations of various instrument types for ABL monitoring and provides an overview on the vast number of retrieval methods developed for the detection of ABL sub-layer heights from different atmospheric quantities (temperature, humidity, wind, turbulence, aerosol). It is outlined how the diurnal evolution of the ABL can be monitored effectively with a combination of methods, pointing out where instrumental or methodological synergy are considered particularly promising. The review highlights the fact that harmonised data acquisition across carefully designed sensor networks as well as tailored data processing are key to obtaining high-quality products that are again essential to capture the spatial and temporal complexity of the lowest part of the atmosphere in which we live and breathe. [ABSTRACT FROM AUTHOR]

The Weather Research and Forecasting model coupled with Chemistry (WRF-Chem) is employed as an intercomparison tool for validating TROPOspheric Monitoring Instrument (TROPOMI) satellite NO 2 retrievals against high-resolution Airborne Prism EXperiment (APEX) remote sensing observations performed in June 2019 in the region of Antwerp, a major hotspot of NO 2 pollution in Europe. The model is first evaluated using meteorological and chemical observations in this area. Sensitivity simulations varying the model planetary layer boundary (PBL) parameterization were conducted for a 3 d period in June 2019, indicating a generally good performance of most parameterizations against meteorological data (namely ceilometer, surface meteorology, and balloon measurements), except for a moderate overestimation (∼ 1 m s -1) of near-surface wind speed. On average, all but one of the PBL schemes reproduce the surface NO 2 measurements at stations of the Belgian Interregional Environmental Agency fairly well, although surface NO 2 is generally underestimated during the day (between -4.3 % and -25.1 % on average) and overestimated at night (8.2 %–77.3 %). This discrepancy in the diurnal evolution arises despite (1) implementing a detailed representation of the diurnal cycle of emissions (Crippa et al., 2020) and (2) correcting the modeled concentrations to account for measurement interferences due to NO y reservoir species, which increases NO 2 concentrations by about 20 % during the day. The model is further evaluated by comparing a 15 d simulation with surface NO 2 , NO, CO, and O 3 data in the Antwerp region. The modeled daytime NO 2 concentrations are more negatively biased during weekdays than during weekends, indicating a misrepresentation of the weekly temporal profile applied to the emissions obtained from Crippa et al. (2020). Using a mass balance approach, we determined a new weekly profile of NO x emissions, leading to a homogenization of the relative bias among the different weekdays. The ratio of weekend to weekday emissions is significantly lower in this updated profile (0.6) than in the profile based on Crippa et al. (2020; 0.84). Comparisons with remote sensing observations generally show a good reproduction of the spatial patterns of NO 2 columns by the model. The model underestimated both APEX (by ca. -37 %) and TROPOMI columns (ca. -25 %) on 27 June, whereas no significant bias is found on 29 June. The two datasets are intercompared by using the model as an intermediate platform to account for differences in vertical sensitivity through the application of averaging kernels. The derived bias of TROPOMI v1.3.1 NO 2 with respect to APEX is about -10 % for columns between (6–12) × 10 15 molec. cm -2. The obtained bias for TROPOMI v1.3.1 increases with the NO 2 column, following CAPEX=1.217Cv1.3-0.783 × 10 15 molec. cm -2 , in line with previous validation campaigns. The bias is slightly lower for the reprocessed TROPOMI v2.3.1, with CAPEX=1.055CPAL-0.437 × 10 15 molec. cm -2 (PAL). Finally, a mass balance approach was used to perform a crude inversion of NO x emissions based on 15 d averaged TROPOMI columns. The emission correction is conducted only in regions with high columns and high sensitivity to emission changes in order to minimize the errors due to wind transport. The results suggest that emissions increase over Brussels–Antwerp (+20 %), the Ruhr Valley (13 %), and especially Paris (+39 %), and emissions decrease above a cluster of power plants in western Germany. [ABSTRACT FROM AUTHOR]

The Sentinel-5P TROPOspheric Monitoring Instrument (TROPOMI) instrument, launched in October 2017, provides unique observations of atmospheric trace gases at a high resolution of about 5 km, with near-daily global coverage, resolving individual sources like thermal powerplants, industrial complexes, fires, medium-scale towns, roads, and shipping routes. Even though Sentinel-5P (S5P) is a global mission, these datasets are especially well suited to test high-resolution regional-scale air quality (AQ) models and provide valuable input for emission inversion systems. In Europe, the Copernicus Atmosphere Monitoring Service (CAMS) has implemented an operational regional AQ forecasting capability based on an ensemble of several European models, available at a resolution of 0.1 ∘ × 0.1 ∘. In this paper, we present comparisons between TROPOMI observations of nitrogen dioxide (NO2) and the CAMS AQ forecasts and analyses of NO2. We discuss the different ways of making these comparisons and present quantitative results in the form of maps for individual days, summer and winter months, and a time series for European subregions and cities between May 2018 and March 2021. The CAMS regional products generally capture the fine-scale daily and averaged features observed by TROPOMI in much detail. In summer, the comparison shows a close agreement between TROPOMI and the CAMS ensemble NO2 tropospheric columns with a relative difference of up to 15 % for most European cities. In winter, however, we find a significant discrepancy in the column amounts over much of Europe, with relative differences up to 50 %. The possible causes for these differences are discussed, focusing on the possible impact of retrieval and modeling errors. Apart from comparisons with the CAMS ensemble, we also present results for comparisons with the individual CAMS models for selected months. Furthermore, we demonstrate the importance of the free tropospheric contribution to the estimation of the tropospheric column and thus include profile information from the CAMS configuration of the ECMWF's (European Centre for Medium-Range Weather Forecasts) global integrated model above 3 km altitude in the comparisons. We also show that replacing the global 1 ∘ × 1 ∘ a priori information in the retrieval by the regional 0.1 ∘ × 0.1 ∘ resolution profiles of CAMS leads to significant changes in the TROPOMI-retrieved tropospheric column, with typical increases at the emission hotspots up to 30 % and smaller increases or decreases elsewhere. As a spinoff, we present a new TROPOMI NO2 level 2 (L2) data product for Europe, based on the replacement of the original TM5-MP generated global a priori profile by the regional CAMS ensemble profile. This European NO2 product is compared with ground-based remote sensing measurements of six Pandora instruments of the Pandonia Global Network and nine Multi-AXis Differential Optical Absorption Spectroscopy (MAX-DOAS) instruments. As compared to the standard S5P tropospheric NO2 column data, the overall bias of the new product for all except two stations is 5 % to 12 % smaller, owing to a reduction in the multiplicative bias. Compared to the CAMS tropospheric NO2 columns, dispersion and correlation parameters with respect to the standard data are, however, superior. [ABSTRACT FROM AUTHOR]

Bromine enrichment (Br enr) has been proposed as an ice core proxy for past sea-ice reconstruction. Understanding the processes that influence bromine preservation in the ice is crucial to achieve a reliable interpretation of ice core signals and to potentially relate them to past sea-ice variability. Here, we present a 210 years bromine record that sheds light on the main processes controlling bromine preservation in the snow and ice at Dome C, East Antarctic plateau. Using observations alongside a modelling approach, we demonstrate that the bromine signal is preserved at Dome C and it is not affected by the strong variations in ultraviolet radiation reaching the Antarctic plateau due to the stratospheric ozone hole. Based on this, we investigate whether the Dome C Br enr record can be used as an effective tracer of past Antarctic sea ice. Due to the limited time window covered by satellite measurements and the low sea-ice variability observed during the last 30 years in East Antarctica, we cannot fully validate Br enr as an effective proxy for past sea-ice reconstructions at Dome C. [ABSTRACT FROM AUTHOR]

Satellite observations of tropospheric NO 2 columns can provide top-down observational constraints on emissions estimates of nitrogen oxides (NOx). Mass-balance-based methods are often applied for this purpose but do not isolate near-surface emissions from those aloft, such as lightning emissions. Here, we introduce an inverse modeling framework that couples satellite chemical data assimilation to a chemical transport model. In the framework, satellite-constrained emissions totals are inferred using model simulations with and without data assimilation in the iterative finite-difference mass-balance method. The approach improves the finite-difference mass-balance inversion by isolating the near-surface emissions increment. We apply the framework to separately estimate lightning and anthropogenic NOx emissions over the Northern Hemisphere for 2019. Using overlapping observations from the Ozone Monitoring Instrument (OMI) and the Tropospheric Monitoring Instrument (TROPOMI), we compare separate NOx emissions inferences from these satellite instruments, as well as the impacts of emissions changes on modeled NO 2 and O 3. OMI inferences of anthropogenic emissions consistently lead to larger emissions than TROPOMI inferences, attributed to a low bias in TROPOMI NO 2 retrievals. Updated lightning NOx emissions from either satellite improve the chemical transport model's low tropospheric O 3 bias. The combined lighting and anthropogenic emissions updates improve the model's ability to reproduce measured ozone by adjusting natural, long-range, and local pollution contributions. Thus, the framework informs and supports the design of domestic and international control strategies. [ABSTRACT FROM AUTHOR]

Polar stratospheric clouds (PSCs) are an important component of ozone chemistry in polar regions. Studying the ozone-depleting processes requires a precise description of PSCs on a long-term basis. Although satellite observations already yield high spatial coverage, continuous ground-based measurements covering long time periods can be a valuable complement. In this study, differential optical absorption spectroscopy (DOAS) instruments are used to investigate the occurrence of PSCs based on the so-called colour index (CI), i.e. the colour of the zenith sky. Defined as the ratio between the observed intensities of scattered sunlight at two wavelengths, it provides a method to detect PSCs during twilight even in the presence of tropospheric clouds. We present data from instruments at the German research station Neumayer, Antarctica (71 ∘ S, 8 ∘ W), as well as Kiruna, Sweden (68 ∘ N, 20 ∘ E), which have been in operation for more than 20 years. For a comprehensive interpretation of the measurement data, the well-established radiative transfer model McArtim is used and radiances of scattered sunlight are simulated at several wavelengths for different solar zenith angles and various atmospheric conditions. The aim is to improve and evaluate the potential of this method. It is then used to infer the seasonal cycle and the variability of PSC occurrence throughout the time series measured in both hemispheres. A good agreement is found to satellite retrievals with deviations particularly in spring. The unexpectedly high signal observed in the DOAS data during springtime suggests the influence of volcanic aerosol. This is also indicated by enhanced aerosol extinction as seen from OMPS (Ozone Mapping and Profiler Suite) data but is not captured by other PSC climatologies. The presented approach allows the detection of PSCs for various atmospheric conditions not only for individual case studies but over entire time series, which is a decisive advance compared to previous work on the PSC detection by ground-based instruments. Apart from the interannual variability, no significant trend is detected for either measurement station. The averaged PSC relative frequency amounts to about 37 % above the Neumayer station and about 18 % above Kiruna. [ABSTRACT FROM AUTHOR]