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The high concentration of fine particles and gaseous pollutants makes polluted areas, such as the urban setting of North China Plain (NCP) of China, a different environment for new particle formation (NPF) compared to many clean regions. Such conditions also hold for other polluted environments in this region (for instance, the rural area of NCP), yet the underlying mechanisms for NPF remain less understood, owing to the limited observations of particles in the sub−3 nm range. Comprehensive measurements, particularly covering the particle number size distribution down to 1.3 nm, were conducted at a rural background site of Gucheng (GC) in the North China Plain (NCP) from 12 November to 24 December 2018. In total, five NPF events during the 39 effective days of measurements for the campaign were identified, with the mean particle nucleation rate (J1.3) and growth rate (GR1.3–2.4) being 22.0 cm−3 s−1 and 3.9 nm h−1, respectively. During these 5 d, NPF concurrently occurred at an urban site in Beijing. Sharing similar sources and transport paths of air masses arriving at our site to that of urban Beijing, we hypothesize that NPF events during these days in this region might be a regional phenomenon. The simultaneous occurrence of NPF in both places implies that H2SO4-amine nucleation, concluded for urban Beijing there, could probably be the dominating mechanism for NPF at our rural site. The higher concentration of sulfuric acid during many non-event days compared to that of event days indicates that the content of sulfuric acid may not necessarily lead to NPF events under current atmosphere. Only when the condensation sink or coagulation sink was significantly lowered, atmospheric NPF occurred, implying that condensation sinks (CSs) and coagulation sinks (CoagSs) are the dominating factors controlling the occurrence of NPF for the present rural environment of the NCP, which is quite similar to the feature seen in urban Beijing.

Nucleation and condensation associated with biogenic volatile organic compounds (BVOCs) are important aerosol formation pathways, yet their contribution to the upper tropospheric aerosols remains inconclusive, hindering the understanding of aerosol climate effects. Here, we develop new schemes describing these organic aerosol formation processes in the WRF-Chem model and investigate their impact on the abundance of cloud condensation nuclei (CCN) in the upper troposphere (UT) over the Amazon Basin. We find that the new schemes significantly increase the simulated CCN number concentrations in the UT (e.g., up to ~400 cm-3 at 0.52 % supersaturation) and greatly improve the agreement with the aircraft observations. Organic condensation enhances the simulated CCN concentration by 90 % through promoting particle growth, while organic nucleation, by replenishing new particles, contributes an additional 14 %. Deep convection determines the rate of these organic aerosol formation processes in the UT through controlling the upward transport of biogenic precursors (i.e., BVOCs). This finding emphasizes the importance of the biosphere-atmosphere coupling in regulating upper tropospheric aerosol concentrations over the tropical forest and calls for attention to its potential role in anthropogenic climate change.

Purpose The purpose of this paper on the one hand is to reduce the sintering temperature, shorten the sintering time and improve the electrical properties of the sample through the two-step flash sintering method and on the other hand is to study the effect of electric field on the phase structure, microstructure and electrical properties of the flash sintering sample. Design/methodology/approach In this paper, (Mg1/3Ta2/3)0.01Ti0.99O2 giant dielectric ceramics were prepared by conventional sintering and two-step flash sintering, respectively. Further, the effect of electric field (600–750 V/cm) on the electrical properties of (Mg1/3Ta2/3)0.01Ti0.99O2 giant dielectric ceramics was studied. Findings The results show that compared with the conventional sintering, the sintering temperature of the two-step flash sintering can be reduced by 200°C and the sintering time can be shortened by 12 times. All sintered samples were single rutile TiO2 structure. Compared with conventional sintering, two-step flash sintering samples have finer grain size. The two-step flash sintered sample has similar dielectric properties to the conventional sintered sample. The dielectric constant of flash sintered samples decreases with the increase of electric field. When the electric field is 700 V/cm, the ceramic sample has the optimal dielectric properties, where the dielectric constant is approximately 5.5 × 103 and the dielectric loss is about 0.18 at 1 kHz. Impedance spectroscopy analysis shows that the excellent dielectric properties are attributed to the internal barrier layer capacitance model. Originality/value This paper not only provides a new method for the preparation of co-doped TiO2 giant dielectric ceramics but also has great potential in greatly improving efficiency and saving energy.

Australian mega-wildfires in the summer of 2019/20 injected smoke into the stratosphere, causing strong ozone depletion in the lower stratosphere. Here, we model the smoke plume and reproduce its unexpected trajectory toward the middle stratosphere at ~35 km altitude. We show that a smoke-charged vortex (SCV) induced and maintained by absorbing aerosols played a key role in lofting pollutants from the lower stratosphere and nearly doubled the southern hemispheric aerosol burden in the middle stratosphere. The SCV caused a redistribution of stratospheric aerosols, which boosted heterogeneous chemistry in the middle stratosphere and enhanced ozone production, compensating up to 70% of the ozone depletion in the lower stratosphere. As global warming continues, we expect a growing frequency and importance of SCVs in promoting the impacts of wildfires on stratospheric aerosols and chemistry.

Tropospheric ozone (O3) is a key greenhouse gas and pollutant that is receiving increasing attention globally. While there are many sources of tropospheric O3, precursors from human activity (Anthro) and open biomass burning (BB) are the only ones that can be controlled. As such, it is crucial for policymakers to understand the relative contributions of the two. However, determining the contribution of O3 can be challenging as it cannot be directly observed. It must be calculated by chemical transportation model (CTM) simulation which could be biased for unreal emission inventory, or estimated by real observations that assumes too simple chemical and transportation processes.In this paper, we propose a solution by developing a deep learning (DL) model that combines both CTM simulations and observations. The DL model is able to learn a generalized relationship between unobservable O3 contribution from Anthro or BB sectors and observable mixing ratio of tracers simulated by CTM with full chemistry and transportation processes. The DL model then, when applied to observed tracers, could avoid the bias from model to provide an accurate estimation of the contributions in reality.Our results indicate the contribution from BB to tropospheric remote ozone mixing ratio is no larger than that from Anthro emission from a global perspective, even when uncertainties are deliberately tuned to bias BB. Therefore, the reduction of anthropogenic emissions should be the top priority for controlling global background O3 levels, at least for the time period of 2016-2018 studied.

Ultrafine particles (UFP), i.e. particles with an aerodynamic diameter below 100 nm, have a significant impact on public health and the hydrological cycle. Recent studies showed that their ability to penetrate more deeply into the lungs and potentially into the blood stream may cause an increased incidence of cardiovascular and cerebrovascular diseases. Additionally, UFPs significantly contribute to cloud condensation nuclei concentrations. However, knowledge on global distributions of UFPs is scarce.We present a global simulation of UFP concentrations using the ECHAM/MESSy Atmospheric Chemistry Model (EMAC), including tropospheric and middle-atmospheric processes, and the modal aerosol microphysics submodel GMXe. Due to the high sensitivity of UFP concentrations to the size distribution of emitted particles, we derived emission median diameter for primary emissions from various sectors and species based on existing literature. We show the importance of primary emissions and nucleation on UFP concentrations as well as their composition, seasonality and vertical distributions.Model results were evaluated over Europe, the United States, India and China, using particle size distribution and particle number concentration measurements from available datasets and the literature. We obtain reasonable agreement between the model results and observations. However, the highest values of observed, street-level UFP concentrations are systematically underestimated, whereas in rural environments close to urban areas they are generally overestimated by the model. As the relatively coarse global model does not resolve concentration gradients in urban centres and local UFP hotspots, high-resolution data of anthropogenic emissions is used to account for such differences in each model grid box. This downscaling further improves the agreement with observations, decreasing the root mean squared logarithmic error and removing discrepancies associated with air quality and population density gradients within the model grid boxes.

In the past decade, ozone (O3) pollution has become a severe environmental problem in major cities in China. Here, based on available observational records, we investigated the long-term trend of ozone pollution in China during 2014–2020. Ozone concentrations were slightly higher in urban areas than in non-urban areas. During these seven years, the highest ozone concentrations primarily occurred in summer in northern China, and in autumn or spring in southern China. Although ozone precursors, including nitrogen oxides (NOX) and carbon monoxide (CO), continuously decreased, ozone concentrations generally increased throughout the seven years with a slower increasing rate after 2017. The long-term trend of ozone concentrations differed across seasons; especially from 2019 to 2020 when ozone concentrations decreased in summer and increased in winter. To analyze the causes of this observed trend, a photochemical box model was used to investigate the change in ozone sensitivity regime in two representative cities – Beijing and Shanghai. Our model simulations suggest that the summertime ozone sensitivity regime in urban areas of China has changed from a VOC-limited regime to a transition regime during 2014–2020; by 2020, the urban photochemistry is in a transition regime in summer but in a VOC-limited regime in winter. This study helps to understand the distinct trends of ozone in China and provides insights into efficient future ozone control strategies in different regions and seasons.

In the past decade, ozone (O3) pollution has become a severe environmental problem in China's major cities. Here, based on available observational records, we investigated the long-term trend of O3 pollution in China during 2014–2020. The O3 concentrations were slightly higher in urban areas than in non-urban areas. During these 7 years, the highest O3 concentrations primarily occurred during summer in northern China, and during autumn or spring in southern China. Although O3 precursors, including nitrogen oxides (NOx) and carbon monoxide (CO), continuously decreased, O3 concentrations generally increased throughout the 7 years with a slower increasing rate after 2017. The long-term trend of O3 concentrations differed across seasons, especially from 2019 to 2020, when O3 concentrations decreased in summer and increased in winter. To analyse the causes of this observed trend, a photochemical box model was used to investigate the change in the O3 sensitivity regime in two representative cities – Beijing and Shanghai. Our model simulations suggest that the summertime O3 sensitivity regime in urban areas of China has changed from a VOC-limited regime to a transition regime during 2014–2020. By 2020, the urban photochemistry was in a transition regime in summer but in a VOC-limited regime in winter. This study helps to understand the distinct trends of O3 in China and provides insights into efficient future O3 control strategies in different regions and seasons.

Acidity is one essential parameter in determining the aqueous phase physical and chemical processes in the atmosphere and strongly influences the climate, ecological, and health effects of aerosols. Traditionally, aerosol acidity is thought to increase with emissions of atmospheric acidic substances (SO2, NOx, etc.) and decrease with that of alkaline ones (NH3, dust, etc.). However, decade-long observations in southeastern U.S. seem to disagree with this hypothesis: while the emissions of NH3 versus SO2 enhanced by over three times, the predicted aerosol acidity is stable, and the observed particle-phase ammonium-to-sulfate ratio is even decreasing. Here, we investigated into this issue with the recently proposed multiphase buffer theory. We show that historically, there is a transition in the dominant drivers of aerosol acidity in this region. Under the ammonia-poor conditions before ∼2008, the acidity is governed by HSO4–/SO42– buffering and the water self-buffering effect. Under the ammonia-rich conditions after ∼2008, aerosol acidity is mainly buffered by NH4+/NH3. Buffering from the organic acids is negligible in the investigated period. In addition, the observed decrease in ammonium-to-sulfate ratio is due to the increased importance of non-volatile cations, especially after ∼2014. We predict that until ∼2050, the aerosols will remain in the ammonia-buffered regime, and the nitrate will remain largely (>98%) in the gas phase in southeastern U.S.

Nitrous acid (HONO) is an important component of the nitrogen cycle in the atmosphere. Photolysis of HONO generates hydroxyl (OH) radicals and significantly influences the atmospheric oxidative capacity. Early laboratory work discovered that soil nitrite, produced via biological nitrification or denitrification, can be an important HONO source. However, the laboratory-determined chamber HONO fluxes can largely deviate from those in the real world for the same soil sample. Therefore, quantification of soil fluxes of HONO in the atmosphere remains challenging. [HONO]*, the equilibrium gas-phase concentration over the aqueous solution of nitrous acid in the soil, has been suggested as a key parameter for quantifying soil fluxes of HONO; but it has not yet been well-validated and quantified. In this project, we present a method to retrieve [HONO]* by conducting controlled dynamic chamber experiments with soil samples and validate the existence of [HONO]* over the soil. We show that [HONO]* is a soil characteristic, independent of HONO concentrations in the chamber. Therefore, it is reliable to use [HONO]* to quantify soil fluxes of HONO. [HONO]* performs as an indicator of the potential of soil to be a source or a sink for atmospheric HONO and helps to better quantify the role of HONO fluxes of soil in the HONO budget and its implications on the oxidizing capacity in the atmosphere.

The interaction between water vapor and aerosol nanoparticles is important in atmospheric processes. Hygroscopicity of sub-10 nm organic nanoparticles and their concentration-dependent thermodynamic properties (e.g., water activity) in the highly supersaturated concentration range are, however, scarcely available. Here we investigate the size dependence of hygroscopicity of organics (i.e., levoglucosan, D-glucose) in dry particle diameter down to 6 nm using a nano-hygroscopicity tandem differential mobility analyzer (nano-HTDMA). Our results show that there is only weak size-dependent hygroscopic growth of both levoglucosan and D-glucose nanoparticles with diameters down to 20 nm. In the diameter range smaller than 20 nm (down to 6 nm), we observed strong size-dependent hygroscopic growth for D-glucose nanoparticles. The hygroscopic growth factors cannot be determined for levoglucosan below 20 nm due to its evaporation. In addition, we compare hygroscopicity measurements for levoglucosan and D-glucose nanoparticles with E-AIM (standard UNIFAC – functional group activity coefficients), the ideal solution theory, and differential Köhler analysis (DKA) predictions. The ideal solution theory describes the measured hygroscopic growth factors of levoglucosan with diameters down to 20 nm and D-glucose nanoparticles with diameters larger than 60 nm, while E-AIM (standard UNIFAC) can successfully predict the growth factors of D-glucose nanoparticles with diameters from 100 down to 6 nm at RH above 88 %–40 % (e.g., at RH above 88 % for 100 nm D-glucose, at RH above 40 % for 6 nm D-glucose). The use of the DKA method leads to good agreement with measured hygroscopic growth factors of D-glucose aerosol nanoparticles with diameters from 100 down to 6 nm. Predicted water activity for these aqueous organic solutions (i.e., levoglucosan, D-glucose) from different parameterization methods agrees well with observations in the low solute concentration range (< 20 mol kg−1) and starts to deviate from observations in the high solute concentration (> 20 mol kg−1).

The southeastern Atlantic is home to an expansive smoke aerosol plume overlying a large cloud deck for approximately a third of the year. The aerosol plume is mainly attributed to the extensive biomass burning activities that occur in southern Africa. Current Earth system models (ESMs) reveal significant differences in their estimates of regional aerosol radiative effects over this region. Such large differences partially stem from uncertainties in the vertical distribution of aerosols in the troposphere. These uncertainties translate into different aerosol optical depths (AODs) in the planetary boundary layer (PBL) and the free troposphere (FT). This study examines differences of AOD fraction in the FT and AOD differences among ESMs (WRF-CAM5, WRF-FINN, GEOS-Chem, EAM-E3SM, ALADIN, GEOS-FP, and MERRA-2) and aircraft-based measurements from the NASA ObseRvations of Aerosols above CLouds and their intEractionS (ORACLES) field campaign. Models frequently define the PBL as the well-mixed surface-based layer, but this definition misses the upper parts of decoupled PBLs, in which most low-level clouds occur. To account for the presence of decoupled boundary layers in the models, the height of maximum vertical gradient of specific humidity profiles from each model is used to define PBL heights. Results indicate that the monthly mean contribution of AOD in the FT to the total-column AOD ranges from 44 % to 74 % in September 2016 and from 54 % to 71 % in August 2017 within the region bounded by 25∘ S–0∘ N–S and 15∘ W–15∘ E (excluding land) among the ESMs. ALADIN and GEOS-Chem show similar aerosol plume patterns to a derived above-cloud aerosol product from the Moderate Resolution Imaging Spectroradiometer (MODIS) during September 2016, but none of the models show a similar above-cloud plume pattern to MODIS in August 2017. Using the second-generation High Spectral Resolution Lidar (HSRL-2) to derive an aircraft-based constraint on the AOD and the fractional AOD, we found that WRF-CAM5 produces 40 % less AOD than those from the HSRL-2 measurements, but it performs well at separating AOD fraction between the FT and the PBL. AOD fractions in the FT for GEOS-Chem and EAM-E3SM are, respectively, 10 % and 15 % lower than the AOD fractions from the HSRL-2. Their similar mean AODs reflect a cancellation of high and low AOD biases. Compared with aircraft-based observations, GEOS-FP, MERRA-2, and ALADIN produce 24 %–36 % less AOD and tend to misplace more aerosols in the PBL. The models generally underestimate AODs for measured AODs that are above 0.8, indicating their limitations at reproducing high AODs. The differences in the absolute AOD, FT AOD, and the vertical apportioning of AOD in different models highlight the need to continue improving the accuracy of modeled AOD distributions. These differences affect the sign and magnitude of the net aerosol radiative forcing, especially when aerosols are in contact with clouds.

A new global dataset of annual averaged ultrafine particle (UFP) concentrations at the Earth's surface has been developed through numerical simulations using the ECHAM/MESSy Atmospheric Chemistry model (EMAC). Size distributions of emitted particles from the contributing source sectors have been derived based on literature reports. The model results of UFP concentrations are evaluated using particle size distribution and particle number concentration measurements from available datasets and the literature. While we obtain reasonable agreement between the model results and observations (logarithmic scale correlation of r = 0.76 for non-remote, polluted regions), the highest values of observed, street-level UFP concentrations are systematically underestimated, whereas in rural environments close to urban areas the model generally overestimates observed UFP concentrations. As the relatively coarse global model does not resolve concentration gradients in urban centres and industrial UFP hotspots, high-resolution data of anthropogenic emissions is used to account for such differences in each model grid box, obtaining UFP concentrations with unprecedented 0.1° x 0.1° horizontal resolution at the Earth's surface. This observation-guided downscaling further improves the agreement with observations, leading to an increase of the logarithmic scale correlation between observed and simulated UFP concentrations to r = 0.84 in polluted environments (and 0.95 in all regions), a decrease of the root mean squared logarithmic error (from 0.57 to 0.43), and removes discrepancies associated with air quality and population density gradients within the model grid boxes. Model results are made publicly available for studies on public health and other impacts of atmospheric UFPs, and for intercomparison with other regional and global models and datasets. Under review for Atmospheric Chemistry and Physics (ACP)

Black carbon (BC) aerosols play an important role in climate systems. Estimating BC’s radiative effect requires knowledge of its mixing state and light absorption enhancement resulting from coatings by other materials. Observational studies have reported much lower light absorption enhancement factors (Eabs) than expected from laboratory studies and model estimates. This has led to an intensive debate on the true magnitude of BC’s climate impact. We find that the observed, apparently small Eabs cannot reflect the overall effect of BC coatings, as it does not include the persisting absorption enhancement by extremely low-volatility (eLV) organics that remain on the BC particles after passing through thermodenuders. Our observations show that eLV organics are extensively present in BC coatings, with a mass fraction of ∼5%–100%. Accounting for these eLV coatings, the observation estimates of Eabs increase substantially to up to 1.8–2.0. Our results highlight a strong radiative warming effect from atmospheric BC.

Aerosol acidity is a key parameter in atmospheric aqueous chemistry and strongly influences the interactions of air pollutants and the ecosystem. The recently proposed multiphase buffer theory provides a framework to reconstruct long-term trends and spatial variations in aerosol pH based on the effective acid dissociation constant of ammonia (Ka,NH3∗). However, non-ideality in aerosol droplets is a major challenge limiting its broad applications. Here, we introduced a non-ideality correction factor (cni) and investigated its governing factors. We found that besides relative humidity (RH) and temperature, cni is mainly determined by the molar fraction of NO3- in aqueous-phase anions, due to different NH4+ activity coefficients between (NH4)2SO4- and NH4NO3-dominated aerosols. A parameterization method is thus proposed to estimate cni at a given RH, temperature and NO3- fraction, and it is validated against long-term observations and global simulations. In the ammonia-buffered regime, with cni correction, the buffer theory can reproduce well the Ka,NH3∗ predicted by comprehensive thermodynamic models, with a root-mean-square deviation ∼ 0.1 and a correlation coefficient ∼ 1. Note that, while cni is needed to predict Ka,NH3∗ levels, it is usually not the dominant contributor to its variations, as ∼ 90 % of the temporal or spatial variations in Ka,NH3∗ are due to variations in aerosol water and temperature.

For understanding and assessing aerosol–cloud interactions and their impact on climate, reliable measurement data on aerosol particle hygroscopicity and cloud condensation nuclei (CCN) activity are required. The CCN activity of aerosol particles can be determined by scanning particle size and supersaturation (S) in CCN measurements. Compared to an existing differential mobility analyzer (DMA) with CCN activity measurement, a broad supersaturation scanning CCN (BS2-CCN) system, in which particles are exposed to a range of S simultaneously, can measure the CCN activity with a high time resolution. Based on a monotonic relation between the activation supersaturation of aerosol particles (Saerosol) and the activated fraction (Fact) of the BS2-CCN measurement, we can derive κ, a single hygroscopicity parameter, directly. Here, we describe how the BS2-CCN system can be effectively calibrated and which factors can affect the calibration curve (Fact−Saerosol). For calibration, size-resolved CCN measurements with ammonium sulfate and sodium chloride particles are performed under three different thermal gradient (dT) conditions (dT=6, 8, and 10 K). We point out key processes that can affect the calibration curve and thereby need to be considered as follows: first, the shape of the calibration curve is primarily influenced by Smax, the maximum S in the activation tube. We need to determine appropriate Smax depending on the particle size and κ to be investigated. To minimize the effect of multiply charged particles, a small geometric mean diameter (Dg) and geometric standard deviation (σg) in number size distribution are recommended when generating the calibration aerosols. Last, Fact is affected by particle number concentration and has a decreasing rate of 0.02 per 100 cm−3 due to the water consumption in the activation tube. For evaluating the BS2-CCN system, intercomparison experiments between typical DMA-CCN and BS2-CCN measurements were performed with a laboratory-generated aerosol mixture and ambient aerosols. Good agreement of κ values between DMA-CCN and BS2-CCN measurements for both experiments shows that the BS2-CCN system can measure CCN activity well compared to the existing measurement method and can measure a broad range of hygroscopicity distributions with a high time resolution (∼1 s vs. a few minutes for a standard CCN activity measurement). As the hygroscopicity can be used as a proxy for the chemical composition, our method can also serve as a complementary approach for fast and size-resolved detection and estimation of aerosol chemical composition.

The high concentration of fine particles as well as gaseous pollutants makes polluted areas, such as the urban setting of North China Plain (NCP) of China, a different environment for NPF compared to many clean regions. Such conditions also hold for other polluted environments in this region, for instance, the rural area of NCP, yet the underlying mechanisms for NPF remain less understood owing to the limited observations of particles in the sub-3nm range. Comprehensive measurements, particularly covering the particle number size distribution down to 1.34 nm, were conducted at a rural background site of Gucheng (GC) in the North China Plain (NCP) from 12 November to 24 December in 2018. Five NPF events during the 39 effective days of measurements for the campaign were identified, with the mean particle nucleation rate (J1.34) and growth rate (GR1.34-2.4) were 29.1 cm-3·s-1 and 0.54 nm·h-1, respectively. During these five days, NPF concurrently occurred in an urban site in Beijing, indicating that NPF events during these days in this region might be a regional phenomena. This implies that H2SO4-amine nucleation, concluded for urban Beijing there, could also be the dominating mechanism for NPF at our rural site. The condensation sink or coagulation sink for the survival of newly-formed and small clusters are the dominating factor controlling the occurrence of NPF under current atmosphere, whereas the contribution from the available H2SO4 cannot be neglected, either. This feature is slightly different from that of urban Beijing, where CS mainly determines whether NPF takes place or not.

Accurate estimation on reaction nitrogen (Nr) deposition is highly demanded for assessing the impacts on the environment and human beings. This study investigated the wet deposition of inorganic nitrogen (IN) in mainland China by measurements from over 500 sites from five observational networks/databases and ensemble results of eleven chemical transport models (CTMs). Each data source has its focus and limitations and together formed a comprehensive view over China. But the inconsistency among different sources may hinder the appropriate usage of data. Model evaluation results demonstrated the models’ deficiency in simulating the wet NO3- deposition over Southeast China (40% underestimation) and showed an overall underestimation of wet NH4+ deposition over the hotspot regions (5-60% underestimation). A synthesis of this study and twelve reference studies was conducted to quantify the national amount of wet IN deposition. The estimations by CTMs ranged 2.4-3.9 Tg(N) yr-1 for wet NOy deposition and 4-6.7 Tg(N) yr-1 for wet NHx deposition, after adjusting the results with 10-19% underestimations in wet NOy deposition and 1-40% underestimations in wet NHx deposition. The estimations by ground observations ranged 7.1-9 Tg(N) yr-1 for wet NOy deposition and 8-13.1 Tg(N) yr-1 for wet NHx deposition, which were 20-275% higher than the estimation by CTMs, but the results were strongly influenced by the abundances and representative of measurements. Studies using statistical techniques to interpolate site observations predicted 3-5.5 Tg(N) yr-1 for wet NOy deposition and 3.9-7.2 Tg(N) yr-1 for wet NHx deposition. This approach benefited from high accuracy and good robustness of the statistical models, but the uncertainty in the interpolation methods could be a potential drawback.

Nitrogen dioxide (NO2) hydrolysis in deliquesced aerosol particles forms nitrous acid and nitrate and thus impacts air quality, climate, and nitrogen cycle. Traditionally, it is considered to proceed far too slowly in the atmosphere. However, the significance of this process is highly uncertain because kinetic studies have only been made in dilute aqueous solutions, and not under high ionic strength conditions of the aerosol particles. Here, we use laboratory experiments, air quality models, and field measurements to examine the effect of ionic strength on the reaction kinetics of NO2 hydrolysis. We find that high ionic strengths (I) enhance the reaction rate constants (kI) by more than two orders of magnitude compared to that at infinite dilution (kI=0), yielding log10(kI/kI=0) = 0.058I. A state-of-the-art air quality model shows that the enhanced NO2 hydrolysis reduces the negative bias in the simulated concentrations of nitrous acid by 27% on average when compared to field observations over the North China Plain. Rapid NO2 hydrolysis also enhances the levels of nitrous acid in other polluted regions such as North India and further promotes atmospheric oxidation capacity. This study highlights the need to evaluate various reaction kinetics of atmospheric aerosols with high ionic strengths.

To better understand the characteristics of aerosol activation ability and optical properties, a comprehensive airborne campaign was conducted over the North China Plain (NCP) from 8 May to 11 June 2016. Vertical profiles of cloud condensation nuclei (CCN) number concentration (NCCN) and aerosol optical properties were measured simultaneously. Seventy-two-hour air mass back trajectories show that during the campaign, the measurement region was mainly influenced by air masses from the northwest and southeast. Air mass sources, temperature structure, anthropogenic emissions, and terrain distribution are factors influencing NCCN profiles. Cloud condensation nuclei spectra suggest that the ability of aerosol to activate into CCN is stronger in southeasterly air masses than in northwesterly air masses and stronger in the free atmosphere than near the surface. Vertical distributions of the aerosol scattering Ångström exponent (SAE) indicate that aerosols near the surface mainly originate from primary emissions consisting of more fine particles. The long-distance transport decreases SAE and makes it vary more in the free troposphere than near the surface. To parameterize NCCN, the equation NCCN=10β⋅σγ is used to fit the relationship between NCCN and the aerosol scattering coefficient (σ) at 450 nm. The fitting parameters β and γ have linear relationships with the SAE. Empirical estimates of NCCN at 0.7 % water vapor supersaturation (SS) from aerosol optical properties are thus retrieved for the two air masses: NCCN=10-0.22⋅SAE+2.39⋅σ0.30⋅SAE+0.29 for northwesterly air masses and NCCN=10-0.07⋅SAE+2.29⋅σ0.14⋅SAE+0.28 for southeasterly air masses. The estimated NCCN at 0.7 % SS agrees with that measured, although the performance differs between low and high concentrations in the two air masses. The results highlight the important impact of aerosol sources on the empirical estimate of NCCN from aerosol optical properties.

The Amazon Basin is frequently influenced by the trans-Atlantic transport of African dust plumes during its wet season (January–April), which not only interrupts the near-pristine atmospheric condition in that season, but also provides nutrient inputs into the Amazon rainforest associated with dust deposition. The factors controlling the long-range transport (LRT) of African dust towards the Amazon Basin and consequently the overall impact of African dust over the Amazon Basin are not yet well understood. In this study, we use the chemical transport model GEOS-Chem to investigate the impact of the export of African mineral dust upon the Amazon Basin during the period of 2013–2017, constrained by multiple datasets obtained from AERONET, MODIS, as well as Cayenne site and the Amazon Tall Tower Observatory (ATTO) site in the Amazon Basin. With optimized particle mass size distribution (PMSD), the model well captures observed AOD regarding both the mean value as well as the decline rate of the logarithm of AOD over the Atlantic Ocean along the transport path (AOaTP), implying the consistence with observed export efficiency of African dust along the trans-Atlantic transport. With an annual emission of 0.73 ± 0.12 Pg a-1, African dust entering the Amazon Basin has surface concentrations of 5.7 ± 1.3 µg m-3 (up to 15 µg m-3 in the northeast corner) during the wet season, accounting for 47 % ± 5.0 % (up to 70 %) of mass concentrations of total aerosols. The frequency of dust events in the Amazon Basin (defined as when surface dust concentrations reach the threshold of 9 µg m-3 on daily basis) in the wet season is around 18 % averaged over the basin, with maxima over 60 % at the northeast coast. During the dust events, AOD over most of the Amazon Basin is dominated by dust. Observed dust peaks over the Amazon Basin are generally associated with relatively higher African dust emissions (including Sahara and Sahel) and longer lifetime of dust along the trans-Atlantic transport, namely higher export efficiency of African dust across the Atlantic Ocean. Associated with dust deposition, we further estimate annual inputs of 52 ± 8.7, 0.97 ± 0.16 and 21 ± 3.6 mg m-2 a-1 for iron, phosphorus and magnesium deposited into the Amazon rainforest, respectively, which may well compensate the hydrologic losses of nutrients in the forest ecosystem.

Aerosol acidity plays a key role in regulating the chemistry and toxicity of atmospheric aerosol particles. The trend of aerosol pH and its drivers is crucial in understanding the multiphase formation pathways of aerosols. Here, we reported the first trend analysis of aerosol pH from 2011 to 2019 in eastern China, calculated with the ISORROPIA model based on observed gas and aerosol compositions. The implementation of the Air Pollution Prevention and Control Action Plan led to −35.8 %, −37.6 %, −9.6 %, −81.0 % and 1.2 % changes of PM2.5, SO42-, NHx, non-volatile cations (NVCs) and NO3- in the Yangtze River Delta (YRD) region during this period. Different from the drastic changes of aerosol compositions due to the implementation of the Air Pollution Prevention and Control Action Plan, aerosol pH showed a minor change of −0.24 over the 9 years. Besides the multiphase buffer effect, the opposite effects from the changes of SO42- and non-volatile cations played key roles in determining this minor pH trend, contributing to a change of +0.38 and −0.35, respectively. Seasonal variations in aerosol pH were mainly driven by the temperature, while the diurnal variations were driven by both temperature and relative humidity. In the future, SO2, NOx and NH3 emissions are expected to be further reduced by 86.9 %, 74.9 % and 41.7 % in 2050 according to the best health effect pollution control scenario (SSP1-26-BHE). The corresponding aerosol pH in eastern China is estimated to increase by ∼0.19, resulting in 0.04 less NO3- and 0.12 less NH4+ partitioning ratios, which suggests that NH3 and NOx emission controls are effective in mitigating haze pollution in eastern China.

A warming climate is one of the most important driving forces of intensified wildfires globally. The unprecedented wildfires broke out in the Australian 'Black Summer' (November 2019-February 2020), which released massive heat, gases, and particles into the atmosphere. The total carbon dioxide (CO

Soil was proposed as an important nitrous acid (HONO) source but has not so far been demonstrated by field flux measurements and its atmospheric impacts are highly uncertain. Through field flux measurements we found strong soil HONO emission flux (FHONO) enhanced by nitrogen fertilizer use for agricultural fields. FHONO showed distinct diurnal variations with noontime peaks up to hundreds of ng-N m-2 s-1. With soil samples where field measurements took place, our laboratory experiments subsequently found that the release of soil nitrification-originated nitrite as HONO was largely accelerated by surface water exchange. This process was parameterized by a modified Arrhenius equation that reproduced field flux observations well. With the consideration of FHONO, the box model could well reproduce the observed ambient HONO and found that FHONO could significantly accelerate ozone production, highlighting the amplified role of nitrogen fertilizer in exacerbating regional ozone pollution. Moreover, we found that nitrification inhibitors could reduce HONO emissions by ~90%, indicating their great potential to mitigate air pollution. Furthermore, we estimated yearly HONO emission of 0.25 Tg-N from global fertilizer use for agriculture, representing a considerable reactive nitrogen source and significantly affecting atmospheric oxidizing capacity and air quality on a global scale.

Biomass burning is one of the key sources of urban aerosols in the North China Plain, especially in winter when the impact of secondary organic aerosols (SOA) formed from biogenic volatile organic compounds (BVOCs) is generally considered to be minor. However, little is known about the influence of biogenic SOA loading on the molecular composition of wintertime organic aerosols. Here, we investigated the water-soluble organic compounds in fine particles (PM2.5) from urban Tianjin by ultrahigh-resolution Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR MS). Our results show that most of the CHO and CHON compounds were derived from biomass burning; they contain O-poor and highly unsaturated compounds with aromatic rings, which are sensitive to photochemical reactions, and some of which probably contribute to light-absorbing chromophores. Under moderate to high SOA loading conditions, the nocturnal chemistry is more efficient than photooxidation to generate secondary CHO and CHON compounds with high oxygen content. Under low SOA-loading, secondary CHO and CHON compounds with low oxygen content are mainly formed by photochemistry. Secondary CHO compounds are mainly derived from oxidation of monoterpenes. But nocturnal chemistry may be more productive to sesquiterpene-derived CHON compounds. In contrast, the number- and intensity-weight of S-containing groups (CHOS and CHONS) increased significantly with the increase of biogenic SOA-loading, which agrees with the fact that a majority of the S-containing groups are identified as organosulfates and nitrooxy-organosulfates that are derived from the oxidation of BVOCs. Terpenes may be potential major contributors to the chemical diversity of organosulfates and nitrooxy-organosulfates under photo-oxidation. While the nocturnal chemistry is more beneficial to the formation of organosulfates and nitrooxy-organosulfates under low SOA-loading. The SOA-loading is an important factor associating with the oxidation degree, nitrate group content and chemodiversity of nitrooxy-organosulfates. Furthermore, our study suggests that the hydrolysis of nitrooxy-organosulfates is a possible pathway for the formation of organosulfates.

Soil was proposed as an important nitrous acid (HONO) source but has not so far been demonstrated by field flux measurements and its atmospheric impacts are highly uncertain. Here we conducted field flux measurements and found that soil HONO emission flux (FHONO) could be enhanced by more than two orders of magnitude by the use of nitrogen fertilizers for agricultural fields in the North China Plain (NCP). FHONO showed distinct diurnal variations with noontime peaks up to hundreds of ng-N m-2 s-1. With soil samples where field measurements took place, our laboratory experiments subsequently found that the release of soil nitrification-originated nitrite as HONO was largely accelerated by soil surface water evaporation. This process was parameterized by a modified Arrhenius equation that reproduced field flux observations well. With the consideration of FHONO, the box model could well reproduce the observed ambient HONO and found that FHONO could significantly accelerate ozone (O3) production, highlighting the amplified role of nitrogen fertilizer use in exacerbating O3 pollution in the NCP. Moreover, we estimated yearly HONO emission of 0.25 Tg-N from global fertilizer use for agriculture, representing a considerable reactive nitrogen source and significantly affecting atmospheric oxidizing capacity and air quality on a global scale. Furthermore, we found that nitrification inhibitors could reduce HONO and nitric oxide emissions by ~90%, indicating their great potential to mitigate regional air pollution.