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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.

Little is known about the formation processes of nitrooxy organosulfates (OSs) by nighttime chemistry. Here we characterize nitrooxy OSs at a molecular level in firework-related aerosols in urban Beijing during Chinese New Year. High-molecular-weight nitrooxy OSs with relatively low H / C and O / C ratios and high unsaturation are potentially aromatic-like nitrooxy OSs. They considerably increased during New Year's Eve, affected by the firework emissions. We find that large quantities of carboxylic-rich alicyclic molecules possibly formed by nighttime reactions. The sufficient abundance of aliphatic-like and aromatic-like nitrooxy OSs in firework-related aerosols demonstrates that anthropogenic volatile organic compounds are important precursors of urban secondary organic aerosols (SOAs). In addition, more than 98 % of those nitrooxy OSs are extremely low-volatility organic compounds that can easily partition into and consist in the particle phase and affect the volatility, hygroscopicity, and even toxicity of urban aerosols. Our study provides new insights into the formation of nitrooxy organosulfates from anthropogenic emissions through nighttime chemistry in the urban atmosphere.

China has made great efforts to monitor and control air pollution in the past decade. Comprehensive characterization and understanding of pollutants in three-dimensions are, however, still lacking. Here, we used data from an observation network consisting of 13 aerosol lidars and more than 1000 ground observation stations combined with a data assimilation technique to conduct a comprehensive analysis of extreme heavy aerosol pollution (HAP) over the North China Plain (NCP) from November–December 2017. During the studied period, the maximum hourly mass concentration of surface PM2.5 reached ∼390 µg m−3. After assimilation, the correlation between model results and the independent observation sub-dataset was ∼50 % higher than that without the assimilation, and the root mean square error was reduced by ∼40 %. From pollution development to dissipation, we divided the HAP in the NCP (especially in Beijing) into four phases: an early phase (EP), a transport phase (TP), an accumulation phase (AP), and a removal phase (RP). We then analyzed the evolutionary characteristics of PM2.5 concentration during different phases on the surface and in 3-D space. We found that the particles were mainly transported from south to north at a height of 1–2 km (during EP and RP) and near the surface (during TP and AP). The amounts of PM2.5 advected into Beijing with the maximum transport flux intensity (TFI) were through the pathways in the relative order of the southwest > southeast > east pathways. The dissipation of PM2.5 in the RP stage (with negative TFI) was mainly from north to south with an average transport height of ∼1 km above the surface. Our results quantified the multi-dimensional distribution and evolution of PM2.5 concentration over the NCP, which may help policymakers develop efficient air pollution control strategies.

We present shipborne measurements of NOx (≡ NO + NO2) and NOy (≡ NOx+ gas- and particle-phase organic and inorganic oxides of nitrogen) in summer 2017 as part of the expedition “Air Quality and climate change in the Arabian BAsin” (AQABA). The NOx and NOz (≡ NOy-NOx) measurements, made with a thermal dissociation cavity ring-down spectrometer (TD-CRDS), were used to examine the chemical mechanisms involved in the processing of primary NOx emissions and their influence on the NOy budget in chemically distinct marine environments, including the Mediterranean Sea, the Red Sea, and the Arabian Gulf, which were influenced to varying extents by emissions from shipping and oil and gas production. Complementing the TD-CRDS measurements, NO and NO2 data sets from a chemiluminescence detector (CLD) were used in the analysis. In all regions, we find that NOx is strongly connected to ship emissions, both via direct emission of NO and via the formation of HONO and its subsequent photolytic conversion to NO. The role of HONO was assessed by calculating the NOx production rate from its photolysis. Mean NO2 lifetimes were 3.9 h in the Mediterranean Sea, 4.0 h in the Arabian Gulf, and 5.0 h in the Red Sea area. The cumulative loss of NO2 during the night (reaction with O3) was more important than daytime losses (reaction with OH) over the Arabian Gulf (by a factor 2.8) and over the Red Sea (factor 2.9), whereas over the Mediterranean Sea, where OH levels were high, daytime losses dominated (factor 2.5). Regional ozone production efficiencies (OPEs; calculated from the correlation between Ox and NOz, where Ox= O3+ NO2) ranged from 10.5 ± 0.9 to 19.1 ± 1.1. This metric quantifies the relative strength of photochemical O3 production from NOx compared to the competing sequestering into NOz species. The largest values were found over the Arabian Gulf, consistent with high levels of O3 found in that region (10–90 percentiles range: 23–108 ppbv). The fractional contribution of individual NOz species to NOy exhibited a large regional variability, with HNO3 generally the dominant component (on average 33 % of NOy) with significant contributions from organic nitrates (11 %) and particulate nitrates in the PM1 size range (8 %).

Conspectus Atmospheric aerosols and fine particulate matter (PM2.5) are strongly affecting human health and climate in the Anthropocene, that is, in the current era of globally pervasive and rapidly increasing human influence on planet Earth. Poor air quality associated with high aerosol concentrations is among the leading health risks worldwide, causing millions of attributable excess deaths and years of life lost every year. Besides their health impact, aerosols are also influencing climate through interactions with clouds and solar radiation with an estimated negative total effective radiative forcing that may compensate about half of the positive radiative forcing of carbon dioxide but exhibits a much larger uncertainty. Heterogeneous and multiphase chemical reactions on the surface and in the bulk of solid, semisolid, and liquid aerosol particles have been recognized to influence aerosol formation and transformation and thus their environmental effects. However, atmospheric multiphase chemistry is not well understood because of its intrinsic complexity of dealing with the matter in multiple phases and the difficulties of distinguishing its effect from that of gas phase reactions. Recently, research on atmospheric multiphase chemistry received a boost from the growing interest in understanding severe haze formation of very high PM2.5 concentrations in polluted megacities and densely populated regions. State-of-the-art models suggest that the gas phase reactions, however, are not capturing the high concentrations and rapid increase of PM2.5 observed during haze events, suggesting a gap in our understanding of the chemical mechanisms of aerosol formation. These haze events are characterized by high concentrations of aerosol particles and high humidity, especially favoring multiphase chemistry. In this Account, we review recent advances that we have made, as well as current challenges and future perspectives for research on multiphase chemical processes involved in atmospheric aerosol formation and transformation. We focus on the following questions: what are the key reaction pathways leading to aerosol formation under polluted conditions, what is the relative importance of multiphase chemistry versus gas-phase chemistry, and what are the implications for the development of efficient and reliable air quality control strategies? In particular, we discuss advances and challenges related to different chemical regimes of sulfate, nitrate, and secondary organic aerosols (SOAs) under haze conditions, and we synthesize new insights into the influence of aerosol water content, aerosol pH, phase state, and nanoparticle size effects. Overall, there is increasing evidence that multiphase chemistry plays an important role in aerosol formation during haze events. In contrast to the gas phase photochemical reactions, which are self-buffered against heavy pollution, multiphase reactions have a positive feedback mechanism, where higher particle matter levels accelerate multiphase production, which further increases the aerosol concentration resulting in a series of record-breaking pollution events. We discuss perspectives to fill the gap of the current understanding of atmospheric multiphase reactions that involve multiple physical and chemical processes from bulk to nanoscale and from regional to global scales. A synthetic approach combining laboratory experiments, field measurements, instrument development, and model simulations is suggested as a roadmap to advance future research.

Volatile organic compounds (VOCs) regulate atmospheric oxidation capacity, and the reactions of VOCs are key in understanding ozone formation and its mitigation strategies. When evaluating its impact, most previous studies did not fully consider the role of oxygenated VOCs due to limitations of measurement technology. By using a proton-transfer-reaction time-of-flight mass spectrometer (PTR-ToF-MS) combined with gas chromatography mass spectrometer (GC-MS) technology, we are able to quantify a large number of oxygenated VOCs in a representative urban environment in southern China. Based on the new dataset, we find that non – formaldehyde (HCHO) OVOCs can contribute large fractions (22–44 %) of total ROX radical production, comparable or larger than the contributions from nitrous acid and formaldehyde. We demonstrate that constraints using OVOCs observations are essential in modeling radical and ozone production, as modelled OVOCs can be substantially lower than measurements, potentially due to primary emissions and/or missing secondary sources. Our results show that models without OVOC constraints using ambient measurements will underestimate P(ROX) and ozone production rate, and may also affect the determination of sensitivity regime in ozone formation. Therefore, a thorough quantification of photodegradable OVOCs species is in urgent need to understand accurately the ozone chemistry and to develop effective control strategies.

The hygroscopicity of organic aerosol (OA) is important for investigation of its climatic and environmental impacts. However, the hygroscopicity parameter κOA remains poorly characterized, especially in the relatively polluted environment on the North China Plain (NCP). Here we conducted simultaneous wintertime measurements of bulk aerosol chemical compositions of PM2.5 and PM1 and bulk aerosol hygroscopicity of PM10 and PM1 on the NCP using a capture-vaporizer time-of-flight aerosol chemical speciation monitor (CV-ToF-ACSM) and a humidified nephelometer system which measures the aerosol light-scattering enhancement factor f(RH). A method for calculating κOA based on f(RH) and bulk aerosol chemical-composition measurements was developed. We found that κOA varied in a wide range with significant diurnal variations. The derived κOA ranged from almost 0.0 to 0.25, with an average (±1σ) of 0.08 (±0.06) for the entire study. The derived κOA was highly correlated with f44 (fraction of m∕z 44 in OA measured by CV-ToF-ACSM), an indicator of the oxidation degree of OA (R=0.79), and the relationship can be parameterized as κOA=1.04×f44-0.02 (κOA=0.3×O:C-0.02, based on the relationship between the f44 and O∕C ratio for CV-ToF-ACSM). On average, κOA reached the minimum (0.02) in the morning near 07:30 local time (LT) and then increased rapidly, reaching the peak value of 0.16 near 14:30 LT. The diurnal variations in κOA were highly and positively correlated with those of mass fractions of oxygenated OA (R=0.95), indicating that photochemical processing played a dominant role in the increase in κOA in winter on the NCP. Results in this study demonstrate the potential wide applications of a humidified nephelometer system together with aerosol composition measurements for investigating the hygroscopicity of OA in various environments and highlight that the parameterization of κOA as a function of OA aging processes needs to be considered in chemical transport models for better evaluating the impacts of OA on cloud formation, atmospheric chemistry, and radiative forcing.

Quantifying the relative importance of gas uptake on the ground and aerosol surfaces helps to determine which processes should be included in atmospheric chemistry models. Gas uptake by aerosols is often characterized by an effective uptake coefficient (γeff), whereas gas uptake on the ground is usually described by a deposition velocity (Vd). For efficient comparison, we introduce an equivalent uptake coefficient (γeqv) at which the uptake flux of aerosols would equal that on the ground surface. If γeff is similar to or larger than γeqv, aerosol uptake is important and should be included in atmospheric models. In this study, we compare uptake fluxes in the planetary boundary layer (PBL) for different reactive trace gases (O3, NO2, SO2, N2O5, HNO3 and H2O2), aerosol types (mineral dust, soot, organic aerosol and sea salt aerosol), environments (urban areas, agricultural land, the Amazon forest and water bodies), seasons and mixing heights. For all investigated gases, γeqv ranges from magnitudes of 10−6–10−4 in polluted urban environments to 10−4–10−1 under pristine forest conditions. In urban areas, aerosol uptake is relevant for all species (γeff≥γeqv) and should be considered in models. On the contrary, contributions of aerosol uptakes in the Amazon forest are minor compared with the dry deposition. The phase state of aerosols could be one of the crucial factors influencing the uptake rates. Current models tend to underestimate the O3 uptake on liquid organic aerosols which can be important, especially over regions with γeff≥γeqv. H2O2 uptakes on a variety of aerosols are yet to be measured under laboratory conditions and evaluated. Given the fact that most models have considered the uptakes of these species on the ground surface, we suggest also considering the following processes in atmospheric models: N2O5 uptake by all types of aerosols, HNO3 and SO2 uptake by mineral dust and sea salt aerosols, H2O2 uptake by mineral dust, NO2 uptakes by sea salt aerosols and O3 uptake by liquid organic aerosols.

Effective density is one of the most important physical properties of atmospheric particles. It is closely linked to particle chemical composition and morphology, and could provide special information on particle emissions and aging processes. In this study, size-resolved particle effective density was measured with a combined DMA-CPMA-CPC system in Multiphase chemistry experiment in Fogs and Aerosols in the North China Plain (McFAN) in autumn 2019. With a new developed flexible Gaussian fit algorithm, frequent (77–87 %) bimodal distribution of particle effective density is identified, with a low-density mode (named sub-density mode) accounting for 22–27 % of total observed particles. The prevalence of the sub-density mode is closely related to fresh black carbon (BC) emissions. The geometric mean for the main-density mode (eff,main) increases from 1.18 g cm−3 (50 nm) to 1.37 g cm−3 (300 nm) due to larger fraction of high-density components and more significant restructuring effect at large particle sizes, but decreases from 0.89 g cm−3 (50 nm) to 0.62 g cm−3 (300 nm) for the sub-density mode (eff,sub) ascribed to the agglomerate effect. eff,main and eff,sub show similar diurnal cycles with peaks in the early afternoon, mainly attributed to the increasing mass fraction of high material density components associated with secondary aerosol production, especially of secondary inorganic aerosol (SIA). To investigate the impact of chemical composition, bulk particle effective density was calculated based on measured chemical composition (ρeff,ACSM) and compared with the average effective density at 300 nm (eff,tot,300 nm). The best agreement between the two densities is achieved when assuming a BC effective density of 0.60 g cm−3. The particle effective density is highly dependent on SIA and BC mass fractions. The influence of BC on the effective density is even stronger than SIA, implying the importance and necessity of including BC in the estimate of effective density for ambient particles.

This study aims at comparing the gas-to-particle conversion mechanisms adopted by regional chemical transport models (CTMs). We use the results from twelve regional CTMs from the third phase of the Model Inter-Comparison Study for Asia (MICS-Asia III). The simulations are conducted over East Asia for the whole year of 2010. The models used are WRF-CMAQ (version 4.7.1 and v5.0.2), WRF-Chem (v3.6.1 and v3.7.1), GEOS-Chem, NHM-Chem, NAQPMS and NU-WRF. Measurements from 54 EANET sites, 86 sites of the Air Pollution Indices (API) and 35 local sites, remote sensing products from AERONET and satellite data from MODIS are used to evaluate model performance on PM10, PM2.5 and its components and aerosol optical depth (AOD). To investigate the inter-model differences in secondary aerosol formation, we compare the Sulfur Oxidation Ratio (SOR) and Nitrogen Oxidation Ratio (NOR) values by different models with observations at the EANET sites. The preliminary results show that the inter-model differences in the oxidation ratio (50%) are almost of the same magnitude as those in simulating the concentrations of particles. The results suggest large uncertainties in the gas-particle conversion process in modelling secondary aerosol formation.

Aerosol acidity is a key parameter in atmospheric aqueous chemistry and strongly influence the interactions of air pollutants and ecosystem. The recently proposed multiphase buffer theory provides a framework to reconstruct long-term trends and spatial variations of 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 given RH, temperature and NO3- fraction, and is validated against long-term observations and global simulations. In the ammonia-buffered regime, with cni correction the buffer theory can well reproduce the Ka,NH3* predicted by comprehensive thermodynamic models, with root-mean-square deviation ~0.1 and 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* is due to variations in aerosol water and temperature.

Simultaneous measurements of aerosol hygroscopicity and chemical composition were performed at a suburban site in the North China Plain in winter 2018 using a self-assembled hygroscopic tandem differential mobility analyzer (H-TDMA) and a capture-vaporizer time-of-flight aerosol chemical speciation monitor (CV-ToF-ACSM), respectively. During the experimental period, aerosol particles usually show an external mixture in terms of hygroscopicity, with a less hygroscopic particles mode (LH) and a more hygroscopic mode (MH). The average ensemble mean hygroscopicity parameter (κmean) are 0.16, 0.18, 0.16, and 0.15 for 60, 100, 150, and 200 nm particles, respectively. Two episodes with different RH/T conditions and secondary aerosol formations are distinguished. Higher aerosol hygroscopicity is observed for all measured sizes in the high RH episode (HRH) than in the low RH episode (LRH). In LRH, κ decreases as the particle size increases, which may be explained by the large contribution of non- or less-hygroscopic primary compounds in large particles due to the enhanced domestic heating emissions at low temperature. The number fraction of LH mode at 200 nm even exceeds 50%. Closure analysis is carried out between the HTDMA-measured κ and the ACSM-derived hygroscopicity using different approximations for the hygroscopic parameters of organic compounds (κorg). The results indicate that κorg is less sensitive towards the variation of its oxidation level under HRH conditions but has a stronger O: C-dependency under LRH conditions. The difference in the chemical composition and their corresponding physical properties under different RH/T conditions reflects potentially different formation mechanisms of secondary organic aerosols at those two distinct episodes.

Vertical measurements of aerosol physical-chemical properties have important significance for better addressing the environment and climate effects of atmospheric aerosol. Traditional in-situ vertical observations of those properties are mainly based on aircraft platforms which are costly and restrictive, and not applicable for near-ground (

Improving air quality is an important driving force for China’s move toward clean energy. Since 2017, the “coal-to-gas” and “coal-to-electricity” strategies have been extensively implemented in northern China, aiming at reducing dispersed coal consumption and related air pollution by promoting the use of clean and low-carbon fuels. Our analyses show that on top of meteorological influences, the effective emission mitigation measures achieved an average decrease of fine particulate matter (PM2.5) concentrations of ∼14% in Beijing and surrounding areas (the “2+26” pilot cities) in winter 2017 compared to the same period of 2016, where the dispersed coal control measures contributed ∼60% of the total PM2.5 reductions. However, the localized air quality improvement was accompanied by a contemporaneous ∼15% upsurge of PM2.5 concentrations over large areas in southern China. We find that the pollution transfer that resulted from a shift in emissions was of a high likelihood caused by a natural gas shortage in the south due to the coal-to-gas transition in the north. The overall shortage of natural gas greatly jeopardized the air quality benefits of the coal-to-gas strategy in winter 2017 and reflects structural challenges and potential threats in China’s clean-energy transition. Our finding highlights the importance and necessity of synergy between environmental and energy policymaking to address the grand challenge of an actionable future to achieve the cobenefits of air quality, human health, and climate.

Effective density is one of the most important physical properties of atmospheric aerosol particles, and is linked to particle formation and aging process. Combined characterization of aerosol density, chemical composition, emission and aging processes may provide crucial information for better understanding their interactions and effects on environment and climate. In autumn of 2019, the effective density of sub-micrometer aerosol particles was measured in-situ at a heavily polluted rural site in the North China Plain (NCP). A tandem technique coupling a Centrifugal Particle Mass Analyzer (CPMA) with a differential mobility analyzer (DMA) and a Condensation Particle Counter (CPC) were used to determine the effective density of ambient aerosol particles with diameters of 50, 100, 150, 220 and 300 nm. The probability distribution of effective density exhibits double peak modes in majority cases, with a higher density mode (main-density) and a lower density mode (sub-density). The existence of sub-density particles normally ascribed to freshly emitted or partial aged black carbon (BC) with non-spherical morphology. The number fraction of sub-density mode varies from 4% to 67%, with mean of 22-27% at five particle sizes. Due to the higher aging degree of larger particles, the main-density exhibits an evident ascending trend with particle size. However, the sub-density decreases as mobility size increases, from 0.89 g/cm3 at 50 nm to 0.62 g/cm3 at 300 nm, since larger fresh soot particles usually present a more agglomerated morphology than small particles. A comparison was carried out between the mean effective density at 300 nm and ACSM-derived density using different approximations of BC density. The best agreement is achieved when assuming a BC density of 0.6 g/cm3, indicating that BC typically exists as non-spherical particles with fractal-like or porous morphology in the NCP in cold season.

Biomass burning (BB) aerosols can influence regional and global climate through interactions with radiation, clouds, and precipitation. Here, we investigate the impact of BB aerosols on the energy balance and hydrological cycle over the Amazon Basin during the dry season. We performed WRF-Chem simulations for a range of different BB emission scenarios to explore and characterize nonlinear effects and individual contributions from aerosol–radiation interactions (ARIs) and aerosol–cloud interactions (ACIs). For scenarios representing the lower and upper limits of BB emission estimates for recent years (2002–2016), we obtained total regional BB aerosol radiative forcings of -0.2 and 1.5Wm-2, respectively, showing that the influence of BB aerosols on the regional energy balance can range from modest cooling to strong warming. We find that ACIs dominate at low BB emission rates and low aerosol optical depth (AOD), leading to an increased cloud liquid water path (LWP) and negative radiative forcing, whereas ARIs dominate at high BB emission rates and high AOD, leading to a reduction of LWP and positive radiative forcing. In all scenarios, BB aerosols led to a decrease in the frequency of occurrence and rate of precipitation, caused primarily by ACI effects at low aerosol loading and by ARI effects at high aerosol loading. Overall, our results show that ACIs tend to saturate at high aerosol loading, whereas the strength of ARIs continues to increase and plays a more important role in highly polluted episodes and regions. This should hold not only for BB aerosols over the Amazon, but also for other light-absorbing aerosols such as fossil fuel combustion aerosols in industrialized and densely populated areas. The importance of ARIs at high aerosol loading highlights the need for accurately characterizing aerosol optical properties in the investigation of aerosol effects on clouds, precipitation, and climate.

Nitrous acid (HONO) is an important component of the nitrogen cycle. HONO can also be rapidly photolyzed by actinic radiation to form hydroxyl radicals (OH) and exerts a primary influence on the oxidative capacity of the atmosphere. The sources and sinks of HONO, however, are not fully understood. Soil nitrite, produced via nitrification or denitrification, is an important source for the atmospheric HONO production. [HONO]*, the equilibrium gas phase HONO concentration over the soil, has been suggested as key to understanding the environmental effects of soil fluxes of HONO (Su et al., 2011). But if and how [HONO]* may exist and vary remains an open question. In this project, a measurement method using a dynamic chamber has been developed to derive [HONO]* and the atmospheric soil fluxes of HONO can accordingly be quantified. We demonstrate the existence of [HONO]* and determine its variation in the course of soil drying processes. We show that when [HONO]* is higher than the atmospheric HONO concentration, HONO will be released from soil; otherwise, HONO will be deposited on soil. This work advances the understanding of soil HONO emissions, and the evaluation of its impact on the atmospheric oxidizing capacity and the nitrogen cycling.

Little is known about the formation processes of nitrooxy-organosulfates (nitrooxy-OSs) by nighttime chemistry. Here we characterize nitrooxy-OSs at a molecular level in firework-related aerosols in urban Beijing during Chinese New Year. High-molecular-weight nitrooxy-OSs with relatively low H / C and O / C ratios and high unsaturation, which are potentially aromatic-like nitrooxy-OSs, considerably increased during the New Year’s Eve. We find that large quantities of carboxylic-rich alicyclic molecules possibly formed by nighttime reactions. The sufficient abundance of aliphatic-like and aromatic-like nitrooxy-OSs demonstrates that both anthropogenic and biogenic volatile organic compounds are essential precursors of urban secondary organic aerosols (SOA). Besides, more than 98 % of nitrooxy-OSs were extremely low-volatile organic compounds that could easily partition into and consist in the particle phase, and affected the volatility, hygroscopicity, and even toxicity of urban aerosols. Our study provides new insights into the formation of nitrooxy-organosulfates from anthropogenic emissions through nighttime chemistry in the urban atmosphere.

Airborne transmission is an important transmission pathway for viruses, including SARS-CoV-2. Regions with a higher proportion of people wearing masks show better control of COVID-19, but the effectiveness of masks is still under debate due to their limited and variable efficiencies in removing respiratory particles. Here, we analyze experimental data and perform model calculations to show that this contrast can be explained by the different regimes of abundance of particles and viruses. Because of the large number of particles exhaled during human respiration and vocalization, indoor environments are usually in a particle-rich regime which means that masks cannot prevent the inhalation of large numbers of respiratory particles. Usually, however, only a small fraction of these particles contain viruses, which implies a virus-limited regime where masks can help to keep the number of inhaled viruses below the infectious dose. For SARS-CoV-2, the virus load in the respiratory tract of infectious individuals can vary by 3 to 4 orders of magnitude (5th to 95th percentile), leading to substantial variations in the abundance of airborne virus concentrations and infection risks. Nevertheless, we find that most environments are in a virus-limited regime where masks have a high efficacy in preventing the spread of COVID-19 by aerosol or droplet transmission during short-term exposure. The characteristic contrast between particle-rich and virus-limited regimes explains why face masks are highly efficient in most but not all environments, and why the largest benefits can be achieved by non-linear synergetic effects of combining masks with other preventive measures such as ventilation and social distancing to reduce airborne virus concentrations and the overall risk of infection.

Low clouds play a key role in the Earth-atmosphere energy balance and influence agricultural production and solar-power generation. Smoke aloft has been found to enhance marine stratocumulus through aerosol-cloud interactions, but its role in regions with strong human activities and complex monsoon circulation remains unclear. Here we show that biomass burning aerosols aloft strongly increase the low cloud coverage over both land and ocean in subtropical southeastern Asia. The degree of this enhancement and its spatial extent are comparable to that in the Southeast Atlantic, even though the total biomass burning emissions in Southeast Asia are only one-fifth of those in Southern Africa. We find that a synergetic effect of aerosol-cloud-boundary layer interaction with the monsoon is the main reason for the strong semi-direct effect and enhanced low cloud formation in southeastern Asia., Biomass burning emissions have been shown to influence clouds in the Atlantic, but its influence in other regions is not well known. Here, the authors show that biomass burning aerosols increase the low-cloud cover over subtropical southeastern Asia by a similar magnitude than over the Atlantic.

Biomass burning (BB) aerosols can influence regional and global climate through interactions with radiation, clouds, and precipitation. Here, we investigate the impact of BB aerosols on the energy balance and hydrological cycle over the Amazon Basin during the dry season. We performed WRF-Chem model simulations for a range of different BB emission scenarios to explore and characterize nonlinear effects and individual contributions from aerosol-radiation interactions (ARI) and aerosol-cloud interactions (ACI). The ARI of BB aerosols tend to suppress low-level liquid clouds by local warming and increased evaporation, and to facilitate the formation of high-level ice clouds by enhancing updrafts and condensation at high altitudes. In contrast, the ACI of BB aerosol particles tend to enhance the formation and lifetime of low-level liquid clouds by providing more cloud condensation nuclei (CCN), and to suppress the formation of high-level ice clouds by reducing updrafts and condensable water vapor at high altitudes (> 8 km). For scenarios representing the lower and upper limits of BB emission estimates for recent years (2002–2016), we obtained total BB aerosol radiative forcings of −0.2 W m−2 and 1.5 W m−2, respectively, showing that the influence of BB aerosols on the regional energy balance can range from modest cooling to strong warming. We find that ACI dominate at low BB emission rates and low aerosol optical depth (AOD), leading to an increased cloud liquid water path (LWP) and negative radiative forcing, whereas ARI dominate at high BB emission rates and high AOD, leading to a reduction of LWP and positive radiative forcing. In all scenarios, BB aerosols led to a decrease in the frequency of occurrence and rate of precipitation, caused primarily by ACI effects at low aerosol loading and by ARI effects at high aerosol loading. Overall, our results show that ACI tend to saturate at high aerosol loading, whereas the strength of ARI continues to increase and plays a more important role in highly polluted episodes and regions. This should hold not only for BB aerosols over the Amazon, but also for other light-absorbing aerosols such as fossil fuel combustion aerosols in industrialized and densely populated areas. The importance of ARI at high aerosol loading highlights the need for accurately characterizing aerosol optical properties in the investigation of aerosol effects on clouds, precipitation, and climate.

Black carbon (BC) is the most important light-absorbing species in the atmosphere and has a strong positive direct radiative forcing. In-cloud scavenging is the major way to wash out BC from the atmosphere. Understanding the connection between its physico-chemical properties and scavenging efficiency is therefore a key to evaluate its lifetime, atmospheric burden and spatial distribution. During an intensive field campaign conducted in the North China Plain in 2019, a ground-based counterflow virtual impactor was utilized to separate fog droplets in radiation fog events. BC mass and mixing state of fog droplet residues were online measured with a single particle soot photometer (SP2). In a strong radiation fog event with visibility of about 50 m, more than 20% fog droplets are found to contain a BC core. BC scavenging efficiency is found to be strongly determined by its diameter and mixing state. Driven by different mechanisms, higher scavenging efficiencies up to 10% are observed for larger and smaller BC particles, and the minimum efficiency is found at BC diameter of 120 nm. For large core (>120 nm) BC-containing particles, the scavenging efficiency increases significantly with coating thickness (CT), from about 10% for CT300 nm. Chemical composition may also be a key parameter influencing the scavenging of BC. Based on the observation of 3 fog events, parameterizations of BC scavenging efficiency are also given in this study.

During the EMeRGe campaign we employed a cloud condensation nuclei counter (CCNC) on board the research aircraft HALO. The instrument was located in the CCN-Rack probing together with a single particle soot photometer (SP2) and a multi-impactor for sampling different air masses on silica nitrate substrates. The aerosol particles were sampled through the HALO Aerosol Submicrometer Inlet (HASI). The measurements have been performed with a two column continuous-flow longitudinal thermal-gradient instrument (CCN-200) manufactured by DMT. The CCN-200 measures the CCN number concentration as a function of water vapor supersaturation (S). These measurements are performed by changing S within one column from 0.10 % up to 1.00 % using 12 different supersaturations and keeping S constant within the second column (S = 0.38 %) to ensure baseline data with 1 Hz time resolution. The different supersaturations are created by changing the flow while setting a fixed temperature difference.Purpose of EMeRGe is to quantify and qualify outflows of megacities, as well as their transport and transformation in the atmosphere. Therefore, measurement flights were performed in the European airspace in 2017, probing aerosol properties over cities like London, Barcelona and Rome. In March 2018, the same set of instruments was probing the outflows of Asian megacities like Taipei, Manila and aged pollution from China Mainland. Furthermore, Japanese and South Korean outflows could be probed. The measurements took place in altitudes between 0.3 km and 13 km ASL. The scientific objective is to investigate the effect of different pollution states on aerosol and CCN properties.

Understanding the formation mechanism of severe haze is crucial for the development of efficient pollution control strategy. Recently, multiphase reactions in aerosol water has been suggested as an important source of sulfate aerosol during severe haze (Zheng et al., 2015;Cheng et al., 2016). Though several oxidation mechanisms have been recognized, the dominant oxidation pathway is still under debate reflecting a missing consensus. Based on a model survey with Weather Research and Forecasting model coupled with Chemistry (WRF-Chem), we have investigated the variability of aerosol pH and regimes of sulfate formation through multiphase oxidation during the haze episodes in January of 2013. Our results show a large spatial and temporal variability in the aerosol pH and sulfate formation regimes. Surface aerosol pH shows a clear diurnal variation with low pH during daytime and high pH during night-time for most cases. Aerosol pH tends to decrease with increasing altitude in the lower atmosphere. For the scenario best reproduces the observations in Beijing, NO2, TMI+O2, O3 and H2O2 pathways can all dominate the production of sulfate in specific areas of the Beijing-Tianjin-Hebei (BTH) region. With the increasing height, O3 pathway and gas phase oxidation by OH radicals become more important. Moreover, sensitivity tests also suggest that, emissions of crustal particles, NH3 and soluble iron/manganese have great impacts on aqueous phase chemistry, and should be better constrained in future studies.References:Zheng, G. J., Duan, F. K., Su, H., Ma, Y. L., Cheng, Y., Zheng, B., Zhang, Q., Huang, T., Kimoto, T., Chang, D., Poschl, U., Cheng, Y. F., and He, K. B.: Exploring the severe winter haze in Beijing: the impact of synoptic weather, regional transport and heterogeneous reactions, Atmos. Chem. Phys., 15, 2969-2983, 10.5194/acp-15-2969-2015, 2015.Cheng, Y. F., Zheng, G. J., Wei, C., Mu, Q., Zheng, B., Wang, Z. B., Gao, M., Zhang, Q., He, K. B., Carmichael, G., Poschl, U., and Su, H.: Reactive nitrogen chemistry in aerosol water as a source of sulfate during haze events in China, Sci Adv, 2, e1601530, UNSP e1601530,10.1126/sciadv.1601530, 2016.

Particle production in the upper troposphere has been reported as an important source of aerosol particles and cloud condensation nuclei in pristine environment and tropical regions and exerts significant climate effects. In this work, we develop a new organic nucleation scheme to the WRF-Chem model with extended particle size bins from 1nm to 10μm. We improve on previous coarse-resolution global simulations that approximate the highly oxygenated multifunctional organic compounds (HOMs) in a thermodynamic state by implementing kinetic calculation of HOMs and using fine-grid regional simulations. Sensitivity studies are conducted over the Amazon Basin during the dry season in 2014 to characterize the HOMs-induced new particle formation and identify its key controlling factors in Amazon. The model simulations are evaluated using aircraft observations of profiles of aerosol particles during the 2014 ACRIDICON-CHUVA campaign. We show that the new particle formation occurs mostly at the upper troposphere and modestly in the planetary boundary layer, driven by low temperature and high concentration of biogenic precursors, respectively. Including the HOMs-induced biogenic new particle formation mechanism decreases the model prediction bias of the particle number concentration in the upper troposphere by over 50%, suggesting an important role of the HOMs-induced biogenic new particle formation in the dry season over the Amazon region.

Black carbon (BC) is the most important light absorbing component in the atmosphere and has significant impacts on the climate, environment and public health. Its effects depend not only on its spatial-temporal distribution, but also on its physico-chemical characteristics. Mixing state is one of the most important properties of BC and strongly determines its hygroscopicity and radiative properties. During an intensive field campaign conducted in the North China Plain in winter 2018, mass-based mixing state of BC-containing particles were online measured with a Centrifugal Particle Mass Analyzer and Single Particle Soot Photometer (CPMA-SP2) tandem system. This technique directly provides the mass ratio of non-refractory coating matter to BC core (MR) in individual particles and does not require to assume the density, morphology and refractive index of BC core and coating in data retrieval, therefore has lower uncertainly compared with leading-edge fit technique. In our measurement, the mean number fraction of uncoated (MR=0), thin coated (0RR≥3) BC-containing particle during the campaign were respectively ~10%, ~35% and ~55%, indicating the strong aging process of BC-containing particle in the North China Plain. The median value of MR was much higher in polluted days than clean days, for example, the median value of MR with a particle mass of 8.56 fg (~220 nm in diameter) for polluted and clean days were ~3.2 and ~1.6, respectively. The mixing state of BC-containing particles obtained by different methods were also compared and evaluated.

Reducing black carbon (BC) emissions has been recognized as an efficient way to simultaneously improve air quality and mitigate climate change. However, the benefits of BC emission controls are not well quantified, partly due to a lack of understanding of the changes in BC light absorption as a result of emission reductions. In this work, we discuss the effects of multi-pollutant emission reductions on BC light absorption based on a field campaign study conducted before, during and after the 2014 APEC (Asia-Pacific Economic Cooperation) meeting in Beijing, China. When emission restrictions were in place during APEC, we found that the reduction in the light absorption of BC-containing particles was driven by both the decrease in BC mass concentration and the weakened light-absorption capability of BC. Compared with that before and after APEC, the daytime light absorption of BC-containing particles during APEC was reduced by ∼ 56 %, of which ∼ 48% was contributed by the decrease in BC mass concentration and the remaining ∼ 8 % was contributed by a weakening of light-absorption capability for BC. Based on single-particle soot photometer (SP2) measurements and Mie calculations, we estimated that the light-absorption capability of BC-containing particles with ∼ 80–200 nm refractory BC (rBC) cores in daytime during APEC was reduced by ∼ 6–15 % and ∼ 10–20 % compared with those before and after APEC, respectively. The decrease in BC light-absorption capability could be attributed to less coating material on BC surfaces as a result of the decreased chemical production of secondary aerosols. Compared with that before and after APEC, the mass ratio between the coating materials and rBC core ( ∼ 80–200 nm) during APEC decreased by ∼ 10–30 % and ∼ 31–53 %, respectively, due to reductions in coating precursor emissions, e.g., SO2 and NO2. The results reveal the benefits of emission control on BC light absorption by simultaneously reducing the mass concentration and light-absorption capability of BC, implying that synergetic reduction in multiple-pollutant emissions could benefit both air quality and climate.

The impacts of black carbon (BC) aerosols on air quality, boundary layer dynamics and climate depend not only on the BC mass concentration but also on the light absorption capability of BC. It is well known that the light absorption capability of BC depends on the amount of coating materials (namely other species that condense and coagulate on BC). However, the difference of light absorption capability of ambient BC-containing particles under different air pollution conditions (e.g., clean and polluted conditions) remains unclear due to the complex aging process of BC in the atmosphere. In this work, we investigated the evolution of light absorption capability for BC-containing particles with changing pollution levels in urban Beijing, China. During the campaign period (17 to 30 November 2014), with an increase in PM1 concentration from ∼ 10 to ∼ 230 µg m−3, we found that the mass-weighted averages of the aging degree and theoretical light absorption capability of BC-containing particles increased by ∼ 33 % and ∼ 18 %, respectively, indicating stronger light absorption capability of BC-containing particles under more polluted conditions due to more coating materials on the BC surface. By using an effective emission intensity (EEI) model, we further found that aging during regional transport plays an important role in the difference in the light absorption capability of BC-containing particles under different air pollution levels. During the pollution episode, ∼ 63 % of the BC over Beijing originated from regional sources outside of Beijing. These regionally sourced BC-containing particles were characterized by more coating materials on BC surfaces due to more coating precursors within more polluted air, which contributed ∼  75 % of the increase in theoretical light absorption capability of BC observed in Beijing during the polluted period (PM1 of ∼ 230 µg m−3) compared to that in the clean period (PM1 of ∼ 10 µg m−3). Due to the increase in theoretical light absorption capability of BC associated with air pollution, the direct radiative forcing of BC was estimated to be increased by ∼ 18 % based on a simple radiation transfer model. Our work identified an amplification of theoretical light absorption and direct radiative forcing under a more polluted air environment due to more coating materials on BC. The air pollution control measures may, however, break the amplification effect by reducing emissions of both BC and the coating precursors and achieve co-benefits of both air quality and climate.

This study investigates the impact of aerosol liquid water content (ALWC) and related factors, i.e., relative humidity (RH), aerosol mass concentration (PM2.5), and aerosol hygroscopicity, on aerosol optical properties, based on field measurements made in the Pearl River Delta (PRD) region of China at the surface (1 November 2019 to 21 January 2020) and in the upper boundary layer (the 532-m Guangzhou tower from 1 February to 21 March 2020). In general, temporal variations in the ambient aerosol backscattering coefficient (βp) and ALWC followed each other. However, the surface βp and 532-m βp had generally opposite diurnal variation patterns, caused by dramatic differences in PM2.5 and ambient RH between the surface and the upper boundary layer. The ambient 532-m RH was systematically higher than the surface RH, with the latter having a much pronounced diurnal cycle than the former. The surface PM2.5 concentration was systematically higher than the PM2.5 concentration at 532 m, and their diurnal cycle patterns were overall opposite. These dramatic differences reveal that the atmospheric variables, i.e., ambient RH and the PM2.5 concentration in the upper boundary layer, cannot be directly represented by the same variables at the surface. Vertical variability should be considered. Clear differences in the sensitivities of aerosol light scattering to ambient RH, PM2.5, and aerosol hygroscopicity between the two levels were found and examined. Aerosol chemical composition played a minor role in causing the differences between the two levels. In particular, βp was more sensitive to PM2.5 at the surface level but more to the ambient RH in the upper boundary layer. The larger contribution of aerosol loading to the variability in βp at the surface implies that local emission controls can decrease βp and further improve atmospheric visibility effectively at the surface during winter in the PRD region.

The heterogeneous hydrolysis of N2O5 on the surface of deliquescent aerosol leads to HNO3 formation and acts as a major sink of NOx in the atmosphere during night-time. The reaction constant of this heterogeneous hydrolysis is determined by temperature (T), relative humidity (RH), aerosol particle composition, and the surface area concentration (S). However, these parameters were not comprehensively considered in the parameterization of the heterogeneous hydrolysis of N2O5 in previous mass-based 3-D aerosol modelling studies. In this investigation, we propose a sophisticated parameterization (NewN2O5) of N2O5 heterogeneous hydrolysis with respect to T, RH, aerosol particle compositions, and S based on laboratory experiments. We evaluated closure between NewN2O5 and a state-of-the-art parameterization based on a sectional aerosol treatment. The comparison showed a good linear relationship (R = 0.91) between these two parameterizations. NewN2O5 was incorporated into a 3-D fully online coupled model, COSMO–MUSCAT, with the mass-based aerosol treatment. As a case study, we used the data from the HOPE Melpitz campaign (10–25 September 2013) to validate model performance. Here, we investigated the improvement of nitrate prediction over western and central Europe. The modelled particulate nitrate mass concentrations ([NO3−]) were validated by filter measurements over Germany (Neuglobsow, Schmücke, Zingst, and Melpitz). The modelled [NO3−] was significantly overestimated for this period by a factor of 5–19, with the corrected NH3 emissions (reduced by 50 %) and the original parameterization of N2O5 heterogeneous hydrolysis. The NewN2O5 significantly reduces the overestimation of [NO3−] by ∼ 35 %. Particularly, the overestimation factor was reduced to approximately 1.4 in our case study (12, 17–18 and 25 September 2013) when [NO3−] was dominated by local chemical formations. In our case, the suppression of organic coating was negligible over western and central Europe, with an influence on [NO3−] of less than 2 % on average and 20 % at the most significant moment. To obtain a significant impact of the organic coating effect, N2O5, SOA, and NH3 need to be present when RH is high and T is low. However, those conditions were rarely fulfilled simultaneously over western and central Europe. Hence, the organic coating effect on the reaction probability of N2O5 may not be as significant as expected over western and central Europe.

In recent decade the ambient fine particle (PM2.5) levels have shown a trend of distinct dropping in China, while ground-level ozone concentrations have been increasing in Beijing and many other Chinese mega-cities. The variation pattern in Los Angeles was markedly different, with PM2.5 and ozone decreasing together over past decades. In this study, we utilize observation-based methods to establish the parametric relationship between PM2.5 concentration and key aerosol physical properties (including aerosol optical depth and aerosol surface concentration), and an observation-based 1-D photochemical model to quantify the response of PM2.5 decline in enhancing ground-level ozone pollution over a large PM2.5 concentration range (10-120 μg m-3). We find that the significance of ozone enhancement due to PM2.5 dropping depends on both the PM2.5 levels and optical properties of particles. Ozone formation increased by 37% in 2006-2016 due to PM2.5 dropping in Beijing, while it becomes less important (7%) as PM2.5 reaches below 40 μg/m3, similar to Los Angeles since 1980s. Therefore, the two cities show the convergence of air pollutant characteristics. Hence a control strategy prioritizing reactive volatile organic compound abatement is projected to yield simultaneous ozone and PM2.5 reductions in Beijing, as experienced in Los Angeles.

Isocyanic acid (HNCO) is a potentially toxic atmospheric pollutant, whose atmospheric concentrations are hypothesized to be linked to adverse health effects. An earlier model study estimated that concentrations of isocyanic acid in China are highest around the world. However, measurements of isocyanic acid in ambient air have not been available in China. Two field campaigns were conducted to measure isocyanic acid in ambient air using a high-resolution time-of-flight chemical ionization mass spectrometer (ToF-CIMS) in two different environments in China. The ranges of mixing ratios of isocyanic acid are from below the detection limit (18 pptv) to 2.8 ppbv (5 min average) with the average value of 0.46 ppbv at an urban site of Guangzhou in the Pearl River Delta (PRD) region in fall and from 0.02 to 2.2 ppbv with the average value of 0.37 ppbv at a rural site in the North China Plain (NCP) during wintertime, respectively. These concentrations are significantly higher than previous measurements in North America. The diurnal variations of isocyanic acid are very similar to secondary pollutants (e.g., ozone, formic acid, and nitric acid) in PRD, indicating that isocyanic acid is mainly produced by secondary formation. Both primary emissions and secondary formation account for isocyanic acid in the NCP. The lifetime of isocyanic acid in a lower atmosphere was estimated to be less than 1 day due to the high apparent loss rate caused by deposition at night in PRD. Based on the steady state analysis of isocyanic acid during the daytime, we show that amides are unlikely enough to explain the formation of isocyanic acid in Guangzhou, calling for additional precursors for isocyanic acid. Our measurements of isocyanic acid in two environments of China provide important constraints on the concentrations, sources, and sinks of this pollutant in the atmosphere.

Biomass burning and primary biological aerosol particles account for an important part of urban aerosols. Floods of studies have been conducted on the chemical compositions of fine aerosols (PM2.5) in megacities where the haze pollution is one of the severe environmental issues in China. However, little is known about their size distributions in atmospheric aerosols in the urban boundary layer. Here, size-segregated aerosol samples were collected in Beijing during haze and clear days from April 2017 to January 2018. Three anhydrosugars, six primary saccharides and four sugar alcohols in these samples were identified and quantified by gas chromatography/mass spectrometry (GC/MS). Higher concentrations of a biomass burning tracer, levoglucosan, were detected in autumn and winter than in other seasons. Sucrose, glucose, fructose, mannitol and arabitol were more abundant in the bloom and glowing seasons. A particularly high level of trehalose was found in spring, which was largely associated with the Asian dust outflows. Anhydrosugars, xylose, maltose, inositol and erythritol are mainly present in the fine mode ( µm), while the others showed the coarse-mode preference. The concentrations of measured tracers of biomass burning particles and primary biological particles in the haze events were higher than those in the non-hazy days, with enrichment factors of 2–10. Geometric mean diameters (GMDs) of molecular markers of biomass burning and primary biological aerosols showed that there was no significant difference in the coarse mode (>2.1 µm) between the haze and non-haze samples, while a size shift towards large particles and large GMDs in the fine fraction ( µm) was detected during the hazy days, which highlights that the stable meteorological conditions with high relative humidity in urban Beijing may favor the condensation of organics onto coarse particles.The contributions of reconstructed primary organic carbon (POC) by tracer-based methods from plant debris, fungal spores and biomass burning to aerosol OC in the total-mode particles were in the ranges of 0.09 %–0.30 % (on average 0.21 %), 0.13 %–1.0 % (0.38 %) and 1.2 %–7.5 % (4.5 %), respectively. This study demonstrates that the contribution of biomass burning was significant in Beijing throughout the whole year with the predominance in the fine mode, while the contributions of plant debris and fungal spores dominated in spring and summer in the coarse mode, especially in sizes >5.8 µm. Our observations demonstrate that the sources, abundance and chemical composition of urban aerosol particles are strongly size dependent in Beijing, which is important to better understand the environmental and health effects of urban aerosols and should be considered in air quality and climate models.

Great progress has been made recently in the understanding of the sources and formation mechanisms of atmospheric aerosols at the ground level. However, vertical profiles and sources of size-resolved particulate matter within the urban boundary layer are still lacking. In this study, vertical distribution characteristics of size-segregated particles were investigated at three observation platforms (ground, 118 m and 488 m) on the 610-meter-high Canton Tower in Guangzhou, China. Size-segregated aerosol samples were simultaneously collected at the three levels on the Canton Tower in autumn and winter, respectively. Major aerosol components, including water-soluble ions, organic carbon and elemental carbon, were measured. The results showed that daily average fine-particle concentrations generally decreased with height. Concentrations of sulfate and ammonium in fine particles displayed small vertical gradients and nitrate concentrations increased with height in autumn, while the above chemical components showed greater variations in winter than in autumn. The size distributions of sulfate and ammonium in both seasons were characterized by dominant unimodal droplet modes with a peak at the size range of 0.44–1.0 μm. In autumn, the nitrate size distribution was bi-modal, peaking at 0.44–1.0 μm and 2.5–10 μm, while it was unimodal in winter, implying that the formation mechanisms for nitrate particles were different in the two seasons. Our results suggest droplet mode sulfate and nitrate are likely formed from aqueous-phase reactions and coarse mode nitrate formation is attributed to heterogeneous reactions of gaseous nitric acid on existing sea-derived coarse particles in autumn at the measurement site. The results from pollution cases study further showed that atmospheric aqueous-phase and heterogeneous reactions together with adverse weather conditions, such as temperature inversion and calm wind, resulted in the autumn and winter haze pollution in the PRD region.

The light absorption black carbon (BC) and brown carbon (BrC) are two important sources of uncertainties in radiative forcing estimate. Here we investigated the light absorption enhancement (Eabs) of BC due to coated materials at an urban (Beijing) and a rural site (Gucheng) in North China Plain (NCP) in winter 2019 by using a photoacoustic extinctiometer coupled with a thermodenuder. Our results showed that the average (±1σ) Eabs was 1.32 (±0.15) at the rural site, which was slightly higher than that at the urban site (1.24 ± 0.15). The dependence of Eabs on coating materials was found to be relatively limited at both sites. However, Eabs presented considerable increases as a function of relative humidity below 70%. Further analysis showed that Eabs during non-heating period in Beijing was mainly caused by secondary components, while it was dominantly contributed by enhanced primary emissions in heating season at both sites. In particular, aerosol particles mixed with coal combustion emissions had a large impact on Eabs (>1.40), while the fresh traffic emissions and freshly oxidized secondary OA (SOA) had limited Eabs (1.00–1.23). Although highly aged or aqueous-phase processed SOA coated on BC showed the largest Eabs, their contributions to the bulk absorption enhancement were generally small. We also quantified the absorption of BrC and source contributions. The results showed the BrC absorption at the rural site was nearly twice that of urban site, yet absorption Angstrom exponents were similar. Multiple linear regression analysis highlighted the major sources of BrC being coal combustion emissions and photochemical SOA at both sites with additional biomass burning at the rural site. Overall, our results demonstrated the relatively limited winter light absorption enhancement of BC in different chemical environments in NCP, which needs be considered in regional climate models to improve BC radiative forcing estimates.

The MIX inventory is developed for the years 2008 and 2010 to support the Model Inter-Comparison Study for Asia (MICS-Asia) and the Task Force on Hemispheric Transport of Air Pollution (TF HTAP) by a mosaic of up-to-date regional emission inventories. Emissions are estimated for all major anthropogenic sources in 29 countries and regions in Asia. We conducted detailed comparisons of different regional emission inventories and incorporated the best available ones for each region into the mosaic inventory at a uniform spatial and temporal resolution. Emissions are aggregated to five anthropogenic sectors: power, industry, residential, transportation, and agriculture. We estimate the total Asian emissions of 10 species in 2010 as follows: 51.3 Tg SO2, 52.1 Tg NOx, 336.6 Tg CO, 67.0 Tg NMVOC (non-methane volatile organic compounds), 28.8 Tg NH3, 31.7 Tg PM10, 22.7 Tg PM2.5, 3.5 Tg BC, 8.3 Tg OC, and 17.3 Pg CO2. Emissions from China and India dominate the emissions of Asia for most of the species. We also estimated Asian emissions in 2006 using the same methodology of MIX. The relative change rates of Asian emissions for the period of 2006–2010 are estimated as follows: −8.1 % for SO2, +19.2 % for NOx, +3.9 % for CO, +15.5 % for NMVOC, +1.7 % for NH3, −3.4 % for PM10, −1.6 % for PM2.5, +5.5 % for BC, +1.8 % for OC, and +19.9 % for CO2. Model-ready speciated NMVOC emissions for SAPRC-99 and CB05 mechanisms were developed following a profile-assignment approach. Monthly gridded emissions at a spatial resolution of 0.25° × 0.25° are developed and can be accessed from http://www.meicmodel.org/dataset-mix.

Sea salt aerosol (SSA) is one of the major components of primary aerosols and has significant impact on the formation of secondary inorganic particles mass on a global scale. In this study, the fully online coupled WRF-Chem model was utilized to evaluate the SSA emission scheme and its influence on the nitrate simulation in a case study in Europe during 10–20 September 2013. Meteorological conditions near the surface, wind pattern and thermal stratification structure were well reproduced by the model. Nonetheless, the coarse-mode (PM1 − 10) particle mass concentration was substantially overestimated due to the overestimation of SSA and nitrate. Compared to filter measurements at four EMEP stations (coastal stations: Bilthoven, Kollumerwaard and Vredepeel; inland station: Melpitz), the model overestimated SSA concentrations by a factor of 8–20. We found that this overestimation was mainly caused by overestimated SSA emissions over the North Sea during 16–20 September. Over the coastal regions, SSA was injected into the continental free troposphere through an “aloft bridge” (about 500 to 1000 m above the ground), a result of the different thermodynamic properties and planetary boundary layer (PBL) structure between continental and marine regions. The injected SSA was further transported inland and mixed downward to the surface through downdraft and PBL turbulence. This process extended the influence of SSA to a larger downwind region, leading, for example, to an overestimation of SSA at Melpitz, Germany, by a factor of ∼ 20. As a result, the nitrate partitioning fraction (ratio between particulate nitrate and the summation of particulate nitrate and gas-phase nitric acid) increased by about 20 % for the coarse-mode nitrate due to the overestimation of SSA at Melpitz. However, no significant difference in the partitioning fraction for the fine-mode nitrate was found. About 140 % overestimation of the coarse-mode nitrate resulted from the influence of SSA at Melpitz. In contrast, the overestimation of SSA inhibited the nitrate particle formation in the fine mode by about 20 % because of the increased consumption of precursor by coarse-mode nitrate formation.

Haze episodes occurred in Beijing repeatedly in 2013, resulting in 189 polluted days. These episodes differed in terms of sources, formation processes, and chemical composition and thus required different control policies. Therefore, an overview of the similarities and differences among these episodes is needed. For this purpose, we conducted one-year online observations and developed a program that can simultaneously divide haze episodes and identify their shapes. A total of 73 episodes were identified, and their shapes were linked with synoptic conditions. Pure-haze events dominated in wintertime, whereas mixed haze-dust (PM2.5/PM10 < 60%) and mixed haze-fog (Aerosol Water/PM2.5 ∼ 0.3) events dominated in spring and summer-autumn, respectively. For all types, increase of ratio of PM2.5 in PM10 was typically achieved before PM2.5 reached ∼150 μg/m(3). In all PM2.5 species observed, organic matter (OM) was always the most abundant component (18-60%), but it was rarely the driving factor: its relative contribution usually decreased as the pollution level increased. The only OM-driven episode observed was associated with intensive biomass-burning activities. In comparison, haze evolution generally coincided with increasing sulfur and nitrogen oxidation ratios (SOR and NOR), indicating the enhanced production of secondary inorganic species. Applicability of these conclusions required further tests with simultaneously multisite observations.

The role of aerosolized SARS-CoV-2 viruses in airborne transmission of COVID-19 has been debated. The aerosols are transmitted through breathing and vocalization by infectious subjects. Some authors state that this represents the dominant route of spreading, while others dismiss the option. Here we present an adjustable algorithm to estimate the infection risk for different indoor environments, constrained by published data of human aerosol emissions, SARS-CoV-2 viral loads, infective dose and other parameters. We evaluate typical indoor settings such as an office, a classroom, choir practice, and a reception/party. Our results suggest that aerosols from highly infective subjects can effectively transmit COVID-19 in indoor environments. This &ldquo, highly infective&rdquo, category represents approximately 20% of the patients who tested positive for SARS-CoV-2. We find that &ldquo, super infective&rdquo, subjects, representing the top 5&ndash, 10% of subjects with a positive test, plus an unknown fraction of less&mdash, but still highly infective, high aerosol-emitting subjects&mdash, may cause COVID-19 clusters (&gt, 10 infections). In general, active room ventilation and the ubiquitous wearing of face masks (i.e., by all subjects) may reduce the individual infection risk by a factor of five to ten, similar to high-volume, high-efficiency particulate air (HEPA) filtering. A particularly effective mitigation measure is the use of high-quality masks, which can drastically reduce the indoor infection risk through aerosols.

Cloud condensation nuclei (CCN) play an important role in the formation and evolution of cloud droplets. However, the dataset of global CCN number concentration (NCCN) is still scarce due to the lack of direct CCN measurements, hindering an accurate evaluation of its climate effects. Alternative approaches to determine NCCN have thus been proposed to calculate NCCN based on measurements of other aerosol properties, such as particle number size distribution, bulk aerosol chemical composition and aerosol optical properties. To better understand the interaction between haze pollution and climate, we performed direct CCN measurements in the winter of 2018 at the Gucheng site, a typical polluted suburban site in North China Plain (NCP). The results show that the average CCN concentrations were 3.81 × 103 cm−3, 5.35 × 103 cm−3, 9.74 × 103 cm−3, 1.27 × 104 cm−3, 1.44 × 104 cm−3 at measured supersaturation levels of 0.114%, 0.148%, 0.273%, 0.492% and 0.864%, respectively. Based on these observational data, we have further investigated two methods of calculating NCCN from: (1) bulk aerosol chemical composition and particle number size distribution; (2) bulk aerosol chemical composition and aerosol optical properties. Our results showed that both methods could well reproduce the observed concentration (R2 > 0.88) and variability of NCCN with a 9% to 23% difference in the mean value. Further error analysis shows that the estimated NCCN tends to be underestimated by about 20% during the daytime while overestimated by

The effect of black carbon (BC) on air quality and the climate is still unclear, which is partly because of the poor understanding regarding the BC aging process in the atmosphere. In this work, we developed a new approach to simulate the BC mixing state (i.e., other species coated on the BC surface) based on an emissions inventory and back-trajectory analysis. The model tracks the evolution of the BC aging degree (characterized by the size ratio of the whole particle and BC core) during atmospheric transport. Using the models, we quantified the mass-averaged aging degree of total BC particles transported to a receptor (e.g., an observation site) from various emission origins (i.e., 0.25∘×0.25∘ grids). The simulations showed good agreement with the field measurements, which validated our model calculation. Modeling the aging process of BC during atmospheric transport showed that it was strongly dependent on emission levels. BC particles from extensive emission origins (i.e., polluted regions) were characterized by a higher aging degree during atmospheric transport due to more co-emitted coating precursors. On the other hand, high-emission regions also controlled the aging process of BC particles that were emitted from cleaner regions and passed through these polluted regions during atmospheric transport. The simulations identified the important roles of extensive emission regions in the BC aging process during atmospheric transport, implying the enhanced contributions of extensive emission regions to BC light absorption. This provides a new perspective on the phenomenon of pollution building up in the North China Plain, further demonstrating that this is mainly driven by regional transport and transformation. The simulation of the BC aging degree during atmospheric transport provided more clues for improving air pollution and climate change.

This study investigates the water supply risk of Panjiakou reservoir in the Luanhe River basin of China during 1956–2016 under environmental change. Since the monthly runoff series during 1956–2016 is a time series with change points, it is necessary to find a new stochastic streamflow series generation approach to preserve the statistical characteristics of the original series and to refine the reliability of water supply risk analysis. This paper improves a known stochastic streamflow simulation method of previous research to better reflect the characteristics of series with change points. And this paper simulates the monthly runoff series with change point of Panjiakou reservoir during 1956–2016 by three different methods, including Thomas–Fiering model, copula function stochastic simulation method, and copula function stochastic simulation method with the mixed distribution model. Among the three methods, the copula function stochastic simulation method with the mixed distribution model which is improved on the basis of copula function stochastic simulation method in this study performs best in simulating the observed monthly runoff series during 1956–2016, and the water supply risk indices including reliability (time-based and volume-based), resilience, vulnerability, drought risk index (DRI), and sustainability index (SUI) are evaluated for Panjiakou reservoir and analyzed by using the stochastic simulation results. By comparing with the previous studies, all indicators are between the corresponding results of 1956–1979 and 1980–2016 with stationary inflows; it can be seen that change point seriously affects the water supply risk of Panjiakou reservoir. These results make it easy to formulate water supply strategies and schemes in changing environment for water resources managers.

Organic molecular composition of fine aerosols in the free troposphere is poorly understood. Here, PM2.5 (particles with aerodynamic diameters ≤ 2.5 μm) samples were collected at the summit of Mt. Emei (3080 m a.s.l.) in the Southwestern China on a daytime and nighttime basis during summer 2016 (June–July). The samples were analyzed by solvent-extraction followed by derivatization and gas chromatography/mass spectrometry (GC/MS). Four classes of organic compounds, i.e. n-alkanes, fatty acids, saccharides and lignin/resin acids were measured quantitatively. Fatty acids were found to be the most abundant species with an average concentration of 401 ± 419 ng m−3 (range 25.7–1490 ng m−3) in the daytime, similar to the average concentration at night (399 ± 447 ng m−3, 19.6–1970 ng m−3). However, the concentrations of biomass burning tracers (e.g., levoglucosan), primary biological aerosol tracers (e.g., mannitol and arabitol) and low molecular weight n-alkanes derived from fossil fuel combustion in daytime samples were obviously higher than those in nighttime samples. The results suggest that valley breezes transported a large number of aerosols and their precursors from the ground surface to the summit of Mt. Emei in the daytime. Estimated with tracer-based methods, the contributions of biogenic primary sources (plant debris, fungal spore, and biomass burning) to organic carbon was in the range of 3.28–83.5% (22.0 ± 17.5%) in the daytime and 3.45–37.4% (10.9 ± 8.97%) at night. As the largest contributor, biomass burning was an important anthropogenic/natural source of aerosol particles in the free troposphere over Mt. Emei. Capsule Valley/mountain breeze is an important constraint to the temporal variations in organic aerosols over Mt. Emei.

Significance Unique information about the abundance and evolution of wildfire-emitted black carbon (BC) in the lowermost part of the stratosphere (LMS) was obtained from long-term airborne measurements made in cooperation with Lufthansa through the Civil Aircraft for the Regular Investigation of the atmosphere Based on an Instrument Container (CARIBIC) project, part of the In-service Aircraft for a Global Observing System (IAGOS) framework. Our results demonstrate that wildfires can dramatically increase BC mass concentration in the LMS, substantially enhance regional climate forcing, and are a challenge for model simulations. Climate change is expected to increase the frequency and spread of wildfires. Thus, recording a present-day baseline with extensive and long-term measurements should help to constrain model estimations of the climate impact of BC and foster our fundamental understanding of future climate change., Wildfires inject large amounts of black carbon (BC) particles into the atmosphere, which can reach the lowermost stratosphere (LMS) and cause strong radiative forcing. During a 14-month period of observations on board a passenger aircraft flying between Europe and North America, we found frequent and widespread biomass burning (BB) plumes, influencing 16 of 160 flight hours in the LMS. The average BC mass concentrations in these plumes (∼140 ng·m−3, standard temperature and pressure) were over 20 times higher than the background concentration (∼6 ng·m−3) with more than 100-fold enhanced peak values (up to ∼720 ng·m−3). In the LMS, nearly all BC particles were covered with a thick coating. The average mass equivalent diameter of the BC particle cores was ∼120 nm with a mean coating thickness of ∼150 nm in the BB plume and ∼90 nm with a coating of ∼125 nm in the background. In a BB plume that was encountered twice, we also found a high diameter growth rate of ∼1 nm·h−1 due to the BC particle coatings. The observed high concentrations and thick coatings of BC particles demonstrate that wildfires can induce strong local heating in the LMS and may have a significant influence on the regional radiative forcing of climate.

Extreme haze episodes repeatedly shrouded Beijing during the winter of 2012–2013, causing major environmental and health problems. To better understand these extreme events, we performed a model-assisted analysis of the hourly observation data of PM2.5 and its major chemical compositions. The synthetic analysis shows that (1) the severe winter haze was driven by stable synoptic meteorological conditions over northeastern China, and not by an abrupt increase in anthropogenic emissions. (2) Secondary species, including organics, sulfate, nitrate, and ammonium, were the major constituents of PM2.5 during this period. (3) Due to the dimming effect of high loading of aerosol particles, gaseous oxidant concentrations decreased significantly, suggesting a reduced production of secondary aerosols through gas-phase reactions. Surprisingly, the observational data reveals an enhanced production rate of secondary aerosols, suggesting an important contribution from other formation pathways, most likely heterogeneous reactions. These reactions appeared to be more efficient in producing secondary inorganics aerosols than organic aerosols resulting in a strongly elevated fraction of inorganics during heavily polluted periods. (4) Moreover, we found that high aerosol concentration was a regional phenomenon. The accumulation process of aerosol particles occurred successively from cities southeast of Beijing. The apparent sharp increase in PM2.5 concentration of up to several hundred μg m−3 per hour recorded in Beijing represented rapid recovery from an interruption to the continuous pollution accumulation over the region, rather than purely local chemical production. This suggests that regional transport of pollutants played an important role during these severe pollution events.

Particulate matter (PM) mass concentrations, seasonal cycles, source sector, and source region contributions in Central Asia (CA) are analyzed for the period April 2008–July 2009 using the Sulfur Transport and dEposition Model (STEM) chemical transport model and modeled meteorology from the Weather Research and Forecasting (WRF) model. Predicted aerosol optical depth (AOD) values (annual mean value ~0.2) in CA vary seasonally, with lowest values in the winter. Surface PM2.5 concentrations (annual mean value ~10 μg m−3) also exhibit a seasonal cycle, with peak values and largest variability in the spring/summer, and lowest values and variability in the winter (hourly values from 2 to 90 μg m−3). Surface concentrations of black carbon (BC) (mean value ~0.1 μg m−3) show peak values in the winter. The simulated values are compared to surface measurements of AOD as well as PM2.5, PM10, BC, and organic carbon (OC) mass concentrations at two regional sites in Kyrgyzstan (Lidar Station Teplokluchenka (LST) and Bishkek). The predicted values of AOD and PM mass concentrations and their seasonal cycles are fairly well captured. The carbonaceous aerosols are underpredicted in winter, and analysis suggests that the winter heating emissions are underestimated in the current inventory. Dust, from sources within and outside CA, is a significant component of the PM mass and drives the seasonal cycles of PM and AOD. On an annual basis, the power and industrial sectors are found to be the most important contributors to the anthropogenic portion of PM2.5. Residential combustion and transportation are shown to be the most important sectors for BC. Biomass burning within and outside the region also contributes to elevated PM and BC concentrations. The analysis of the transport pathways and the variations in particulate matter mass and composition in CA demonstrates that this region is strategically located to characterize regional and intercontinental transport of pollutants. Aerosols at these sites are shown to reflect dust, biomass burning, and anthropogenic sources from Europe; South, East, and Central Asia; and Russia depending on the time period. Simulations for a reference 2030 emission scenario based on pollution abatement measures already committed to in current legislation show that PM2.5 and BC concentrations in the region increase, with BC growing more than PM2.5 on a relative basis. This suggests that both the health impacts and the climate warming associated with these particles may increase over the next decades unless additional control measures are taken. The importance of observations in CA to help characterize the changes that are rapidly taking place in the region are discussed.