Search

Soil emissions of nitrogen compounds, including NO and HONO, play a significant role in the atmospheric nitrogen budget. However, HONO has been overlooked in previous research on soil reactive nitrogen (Nr) emissions and their impacts on air quality in China. This study estimates soil NOx and soil HONO emissions (SNOx and SHONO) in North China during July 2018 using an updated soil Nr emissions scheme in a chemical transport model, Unified Inputs (initial and boundary conditions) for Weather Research and Forecasting coupled with Chemistry (UI-WRF-Chem). The effects of soil Nr emissions on O3 pollution, air quality and temperature rise are also studied, with a focus on two key regions, Beijing–Tianjin–Hebei (BTH) and the Fenwei Plain (FWP), known for high soil Nr and anthropogenic emissions. We find that the flux of SNOx is nearly double that of SHONO. The monthly contributions of SNOx and SHONO account, respectively, for 37.3 % and 13.5 % of anthropogenic NOx emissions in BTH and for 29.2 % and 19.2 % in the FWP during July 2018. Soil Nr emissions have a significant impact on surface O3 and nitrate, exceeding SNOx or SHONO effects alone. On average, soil Nr emissions increase maximum daily 8 h (MDA8) O3 by 16.9 % and nitrate concentrations by 42.4 % in BTH, and they increase MDA8 O3 by 17.2 % and nitrate concentrations by 42.7 % in the FWP. Reducing anthropogenic NOx emissions leads to a more substantial suppressive effect of soil Nr emissions on O3 mitigation, particularly in BTH. Soil Nr emissions, through their role as precursors for secondary inorganic aerosols, can result in a slower increase rate of surface air temperature in future emissions reduction scenarios. This study suggests that mitigating O3 pollution and addressing climate change in China should consider the role of soil Nr emissions and their regional differences.

This paper presents large-eddy simulations with atmospheric chemistry of four large point sources world-wide, focusing on the evaluation of NOx (NO + NO2) emissions with the TROPOspheric Monitoring Instrument (TROPOMI). We implemented a condensed chemistry scheme to investigate how the emitted NOx (95 % as NO) is converted to NO2 in the plume. To use NOx as a proxy for CO2 emission, information about its atmospheric lifetime and the fraction of NOx present as NO2 is required. We find that the chemical evolution of the plumes depends strongly on the amount of NOx that is emitted, as well as on wind speed and direction. For large NOx emissions, the chemistry is pushed in a high-NOx chemical regime over a length of almost 100 km downwind of the stack location. Other plumes with lower NOx emissions show a fast transition to an intermediate-NOx chemical regime, with short NOx lifetimes. Simulated NO2 columns mostly agree within 20 % with TROPOMI, signalling that the emissions used in the model were approximately correct. However, variability in the simulations is large, making a one-to-one comparison difficult. We find that temporal wind speed variations should be accounted for in emission estimation methods. Moreover, results indicate that common assumptions about the NO2 lifetime (≈ 4 h) and NOx:NO2 ratios (≈ 1.3) in simplified methods that estimate emissions from NO2 satellite data need revision.

Reliable and robust monitoring tools are crucial to assess the effectiveness of land mitigation techniques (LMTs) in enhancing carbon uptake, enabling informed decision making by policymakers. This study, addressing one of the scientific goals of the EU Horizon 2020 Land Use Based Mitigation for Resilient Climate Pathways (LANDMARC) project, examines the feasibility of using satellite solar-induced fluorescence (SIF) in combination with other satellite data as a monitoring proxy to evaluate the effects of LMTs on carbon uptake. Two distinct cases are explored: (1) instantaneous vegetation destruction caused by a 2019 eucalyptus wildfire in southeast Australia and (2) gradual forest gain resulting from reforestation efforts in northern China in 2007–2012. The cases are monitored using SIF from the TROPOspheric Monitoring Instrument (TROPOMI) and Global Ozone Monitoring Experiment-2A (GOME-2A), respectively. Comparing the temporal variability in SIF across the affected areas and nearby reference areas reveals that vegetation dynamics changed as a consequence of the land-use changes in both cases. Specifically, in the Australia case, TROPOMI demonstrated an immediate reduction in the SIF signal of 0.6 mW m−2 sr−1 nm−1 (−72 %) over the eucalypt forest right after the fire. Exploiting the strong correspondence between TROPOMI SIF and gross primary productivity (GPP) at the nearby representative eddy covariance Tumbarumba site and through the FluxSat product, we estimate that the Australian fire led to a loss in GPP of 130–200 GgC in the first 8 months after the fire. Over the northern Chinese provinces of Gansu, Shaanxi, Sichuan, Chongqing, and Shanxi, we report an increase in GOME-2A summertime SIF of 0.1–0.2 mW m−2 sr−1 nm−1, coinciding with reforestation efforts between 2007 and 2012. This increase in the SIF signal is likely driven by a combination of increasingly favourable natural conditions and by the reforestation effort itself. A multivariate model that takes into account growth factors such as water availability and maximum temperature as well as satellite-derived forest-cover data explains the observed variability in GOME-2A SIF in the Chinese case reasonably well (R2=0.72). The model suggests that increases in both forest cover and soil moisture have led, in step, to the observed increase in vegetation activity over northern China. In that region, for every 100 km2 of additional forest cover, SIF increases by 0.1 mW m−2 sr−1 nm−1 between 2007 and 2012. Our study highlights that the use of satellite-based SIF, together with supporting in situ, modelled, and satellite data, allows us to monitor the impact of LMT implementation on regional carbon uptake as long as the scale of the LMT is of sufficient spatial extent.

The sensitivity of satellites to air pollution close to the sea surface is decreased by the 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 equipped with a sniffer sensor system to measure NOx (= NO + NO2), CO2 and SO2. This instrumentation enabled 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. The aircraft sensor observes multiple clear signatures of ship plumes from seconds after emission to multiple kilometers downwind. Besides that, our results show that the chemical transport model Transport Model 5, Massively Parallel version (TM5-MP), which is used in the retrieval of the operational TROPOMI NO2 data, tends to underestimate surface level pollution – especially under conditions without land outflow – while overestimating NO2 at higher levels over the study region. The higher horizontal resolution in the regional CAMS (Copernicus Atmosphere Monitoring Service) ensemble mean and the LOTOS-EUROS (Long Term Ozone Simulation European Operational Smog) model improves the surface level pollution estimates. However, the models still systematically overestimate NO2 levels at higher altitudes, indicating exaggerated vertical mixing and overall too much NO2 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 make this issue especially relevant over sea and coastal regions.

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.

Satellite-based retrievals of tropospheric NO2 columns are widely used to infer NOx (≡ NO + NO2) emissions. These retrievals rely on model information for the vertical distribution of NO2. The free tropospheric background above 2 km is particularly important because the sensitivity of the retrievals increases with altitude. Free tropospheric NOx also has a strong effect on tropospheric OH and ozone concentrations. Here we use observations from three aircraft campaigns (SEAC4RS, DC3, and ATom) and four atmospheric chemistry models (GEOS-Chem, GMI, TM5, and CAMS) to evaluate the model capabilities for simulating NOx in the free troposphere and attribute it to sources. NO2 measurements during the Studies of Emissions and Atmospheric Composition, Clouds, and Climate Coupling by Regional Surveys (SEAC4RS) and Deep Convective Clouds and Chemistry (DC3) campaigns over the southeastern U.S. in summer show increasing concentrations in the upper troposphere above 10 km, which are not replicated by the GEOS-Chem, although the model is consistent with the NO measurements. Using concurrent NO, NO2, and ozone observations from a DC3 flight in a thunderstorm outflow, we show that the NO2 measurements in the upper troposphere are biased high, plausibly due to interference from thermally labile NO2 reservoirs such as peroxynitric acid (HNO4) and methyl peroxy nitrate (MPN). We find that NO2 concentrations calculated from the NO measurements and NO–NO2 photochemical steady state (PSS) are more reliable to evaluate the vertical profiles of NO2 in models. GEOS-Chem reproduces the shape of the PSS-inferred NO2 profiles throughout the troposphere for SEAC4RS and DC3 but overestimates NO2 concentrations by about a factor of 2. The model underestimates MPN and alkyl nitrate concentrations, suggesting missing organic NOx chemistry. On the other hand, the standard GEOS-Chem model underestimates NO observations from the Atmospheric Tomography Mission (ATom) campaigns over the Pacific and Atlantic oceans, indicating a missing NOx source over the oceans. We find that we can account for this missing source by including in the model the photolysis of particulate nitrate on sea salt aerosols at rates inferred from laboratory studies and field observations of nitrous acid (HONO) over the Atlantic. The median PSS-inferred tropospheric NO2 column density for the ATom campaign is 1.7 ± 0.44 × 1014 molec. cm−2, and the NO2 column density simulated by the four models is in the range of 1.4–2.4 × 1014 molec. cm−2, implying that the uncertainty from using modeled NO2 tropospheric columns over clean areas in the retrievals for stratosphere–troposphere separation is about 1 × 1014 molec. cm−2. We find from GEOS-Chem that lightning is the main primary NOx source in the free troposphere over the tropics and southern midlatitudes, but aircraft emissions dominate at northern midlatitudes in winter and in summer over the oceans. Particulate nitrate photolysis increases ozone concentrations by up to 5 ppbv (parts per billion by volume) in the free troposphere in the northern extratropics in the model, which would largely correct the low model bias relative to ozonesonde observations. Global tropospheric OH concentrations increase by 19 %. The contribution of the free tropospheric background to the tropospheric NO2 columns observed by satellites over the contiguous U.S. increases from 25 ± 11 % in winter to 65 ± 9 % in summer, according to the GEOS-Chem vertical profiles. This needs to be accounted for when deriving NOx emissions from satellite NO2 column measurements.

Quantification and control of NOx and CO2 emissions are essential across the world to limit adverse climate change and improve air quality. We present a new top-down method, an improved superposition column model to estimate day-to-day NOx and CO2 emissions from the large city of Wuhan, China, located in a polluted background. The latest released version 2.3.1 TROPOMI (TROPOspheric Monitoring Instrument) NO2 columns and version 10r of the Orbiting Carbon Observatory-2 (OCO-2)-observed CO2 mixing ratio are employed. We quantified daily NOx and CO2 emissions from Wuhan between September 2019 and October 2020 with an uncertainty of 31 % and 43 %, compared to 39 % and 49 % with the earlier v1.3 TROPOMI data, respectively. Our estimated NOx and CO2 emissions are verified against bottom-up inventories with minor deviations ( % for the 2019 mean, ranging from −20 % to 48 % on a daily basis). Based on the estimated CO2 emissions, we also predicted daily CO2 column mixing ratio enhancements, which match well with OCO-2 observations ( % bias, within ±0.3 ppm). We capture the day-to-day variation of NOx and CO2 emissions from Wuhan in 2019–2020, which does not reveal a substantial “weekend reduction” but does show a clear “holiday reduction” in the NOx and CO2 emissions. Our method also quantifies the abrupt decrease and slow NOx and CO2 emissions rebound due to the Wuhan lockdown in early 2020. This work demonstrates the improved superposition model to be a promising new tool for the quantification of city NOx and CO2 emissions, allowing policymakers to gain real-time information on spatial–temporal emission patterns and the effectiveness of carbon and nitrogen regulation in urban environments.

A new method is presented for estimating urban hydroxyl radical (OH) concentrations using the downwind decay of the ratio of nitrogen dioxide over carbon monoxide column-mixing ratios (XNO2/XCO) retrieved from the Tropospheric Monitoring Instrument (TROPOMI). The method makes use of plumes simulated by the Weather Research and Forecast model (WRF-Chem) using passive-tracer transport, instead of the encoded chemistry, in combination with auxiliary input variables such as Copernicus Atmospheric Monitoring Service (CAMS) OH, Emission Database for Global Atmospheric Research v4.3.2 (EDGAR) NOx and CO emissions, and National Center for Environmental Protection (NCEP)-based meteorological data. NO2 and CO mixing ratios from the CAMS reanalysis are used as initial and lateral boundary conditions. WRF overestimates NO2 plumes close to the center of the city by 15 % to 30 % in summer and 40 % to 50 % in winter compared to TROPOMI observations over Riyadh. WRF-simulated CO plumes differ by 10 % with TROPOMI in both seasons. The differences between WRF and TROPOMI are used to optimize the OH concentration, NOx, CO emissions and their backgrounds using an iterative least-squares method. To estimate OH, WRF is optimized using (a) TROPOMI XNO2/XCO and (b) TROPOMI-derived XNO2 only. For summer, both the NO2/CO ratio optimization and the XNO2 optimization increase the prior OH from CAMS by 32 ± 5.3 % and 28.3 ± 3.9 %, respectively. EDGAR NOx and CO emissions over Riyadh are increased by 42.1 ± 8.4 % and 101 ± 21 %, respectively, in summer. In winter, the optimization method doubles the CO emissions while increasing OH by ∼ 52 ± 14 % and reducing NOx emissions by 15.5 ± 4.1 %. TROPOMI-derived OH concentrations and the pre-existing exponentially modified Gaussian function fit (EMG) method differ by 10 % in summer and winter, confirming that urban OH concentrations can be reliably estimated using the TROPOMI-observed NO2/CO ratio. Additionally, our method can be applied to a single TROPOMI overpass, allowing one to analyze day-to-day variability in OH, NOx and CO emission.

Nitrogen dioxide (NO2) is one of the main data products measured by the Tropospheric Monitoring Instrument (TROPOMI) on the Sentinel-5 Precursor (S5P) satellite, which combines a high signal-to-noise ratio with daily global coverage and high spatial resolution. TROPOMI provides a valuable source of information to monitor emissions from local sources such as power plants, industry, cities, traffic and ships, and variability of these sources in time. Validation exercises of NO2 v1.2–v1.3 data, however, have revealed that TROPOMI's tropospheric vertical column densities (VCDs) are too low by up to 50 % over highly polluted areas. These findings are mainly attributed to biases in the cloud pressure retrieval, the surface albedo climatology and the low resolution of the a priori profiles derived from global simulations of the TM5-MP chemistry model. This study describes improvements in the TROPOMI NO2 retrieval leading to version v2.2, operational since 1 July 2021. Compared to v1.x, the main changes are the following. (1) The NO2-v2.2 data are based on version-2 level-1b (ir)radiance spectra with improved calibration, which results in a small and fairly homogeneous increase in the NO2 slant columns of 3 % to 4 %, most of which ends up as a small increase in the stratospheric columns. (2) The cloud pressures are derived with a new version of the FRESCO cloud retrieval already introduced in NO2-v1.4, which led to a lowering of the cloud pressure, resulting in larger tropospheric NO2 columns over polluted scenes with a small but non-zero cloud coverage. (3) For cloud-free scenes a surface albedo correction is introduced based on the observed reflectance, which also leads to a general increase in the tropospheric NO2 columns over polluted scenes of order 15 %. (4) An outlier removal was implemented in the spectral fit, which increases the number of good-quality retrievals over the South Atlantic Anomaly region and over bright clouds where saturation may occur. (5) Snow/ice information is now obtained from ECMWF weather data, increasing the number of valid retrievals at high latitudes. On average the NO2-v2.2 data have tropospheric VCDs that are between 10 % and 40 % larger than the v1.x data, depending on the level of pollution and season; the largest impact is found at mid and high latitudes in wintertime. This has brought these tropospheric NO2 closer to Ozone Monitoring Instrument (OMI) observations. Ground-based validation shows on average an improvement of the negative bias of the stratospheric (from −6 % to −3 %), tropospheric (from −32 % to −23 %) and total (from −12 % to −5 %) columns. For individual measurement stations, however, the picture is more complex, in particular for the tropospheric and total columns.

TROPOMI (TROPOspheric Monitoring Instrument) measurements of tropospheric NO2 columns provide powerful information on emissions of air pollution by ships on open sea. This information is potentially useful for authorities to help determine the (non-)compliance of ships with increasingly stringent NOx emission regulations. We find that the information quality is improved further by recent upgrades in the TROPOMI cloud retrieval and an optimal data selection. We show that the superior spatial resolution of TROPOMI allows for the detection of several lanes of NO2 pollution ranging from the Aegean Sea near Greece to the Skagerrak in Scandinavia, which have not been detected with other satellite instruments before. Additionally, we demonstrate that under conditions of sun glint TROPOMI's vertical sensitivity to NO2 in the marine boundary layer increases by up to 60 %. The benefits of sun glint are most prominent under clear-sky situations when sea surface winds are low but slightly above zero (±2 m s−1). Beyond spatial resolution and sun glint, we examine for the first time the impact of the recently improved cloud algorithm on the TROPOMI NO2 retrieval quality, both over sea and over land. We find that the new FRESCO+ (Fast Retrieval Scheme for Clouds from the Oxygen A band) wide algorithm leads to 50 hPa lower cloud pressures, correcting a known high bias, and produces 1–4×1015 molec. cm−2 higher retrieved NO2 columns, thereby at least partially correcting for the previously reported low bias in the TROPOMI NO2 product. By training an artificial neural network on the four available periods with standard and FRESCO+ wide test retrievals, we develop a historic, consistent TROPOMI NO2 data set spanning the years 2019 and 2020. This improved data set shows stronger (35 %–75 %) and sharper (10 %–35 %) shipping NO2 signals compared to co-sampled measurements from OMI. We apply our improved data set to investigate the impact of the COVID-19 pandemic on ship NO2 pollution over European seas and find indications that NOx emissions from ships reduced by 10 %–20 % during the beginning of the COVID-19 pandemic in 2020. The reductions in ship NO2 pollution start in March–April 2020, in line with changes in shipping activity inferred from automatic identification system (AIS) data on ship location, speed, and engine.

Dry deposition is an important sink of tropospheric ozone that affects surface concentrations and impacts crop yields, the land carbon sink, and the terrestrial water cycle. Dry deposition pathways include plant uptake via stomata and non-stomatal removal by soils, leaf surfaces, and chemical reactions. Observational studies indicate that ozone deposition exhibits substantial temporal variability that is not reproduced by atmospheric chemistry models due to a simplified representation of vegetation uptake processes in these models. In this study, we explore the importance of stomatal and non-stomatal uptake processes in driving ozone dry deposition variability on diurnal to seasonal timescales. Specifically, we compare two land surface ozone uptake parameterizations – a commonly applied big leaf parameterization (W89; Wesely, 1989) and a multi-layer model (MLC-CHEM) constrained with observations – to multi-year ozone flux observations at two European measurement sites (Ispra, Italy, and Hyytiälä, Finland). We find that W89 cannot reproduce the diurnal cycle in ozone deposition due to a misrepresentation of stomatal and non-stomatal sinks at our two study sites, while MLC-CHEM accurately reproduces the different sink pathways. Evaluation of non-stomatal uptake further corroborates the previously found important roles of wet leaf uptake in the morning under humid conditions and soil uptake during warm conditions. The misrepresentation of stomatal versus non-stomatal uptake in W89 results in an overestimation of growing season cumulative ozone uptake (CUO), a metric for assessments of vegetation ozone damage, by 18 % (Ispra) and 28 % (Hyytiälä), while MLC-CHEM reproduces CUO within 7 % of the observation-inferred values. Our results indicate the need to accurately describe the partitioning of the ozone atmosphere–biosphere flux over the in-canopy stomatal and non-stomatal loss pathways to provide more confidence in atmospheric chemistry model simulations of surface ozone mixing ratios and deposition fluxes for large-scale vegetation ozone impact assessments.