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Aerosol particles play critical roles in climate and human health. However, aerosol composition and evolution, particularly secondary organic aerosol (SOA), and aerosol interactions with clouds in high-altitude background areas in China remain less understood. Here, we conducted real-time measurements of submicron aerosols (PM1) using aerosol mass spectrometers at a forested mountain site (1128 m a.s.l.) in southeastern China in November 2022. The average (±1σ) PM1 mass concentration was 4.3±4.8 µg m−3, which was ubiquitously lower than that at other mountain sites in China. Organic aerosol (OA) constituted the largest fraction of PM1 (42.9 %) and was predominantly secondary, as indicated by the high oxygen-to-carbon (O / C) ratio (0.85–0.96) and carbon oxidation state (0.21–0.49). Notably, the remarkably enhanced PM1 concentrations observed during the daytime on cloudless days were identified to be likely to be produced from cloud evaporation. While more oxidized oxygenated OA was scavenged efficiently during cloud events, cloud evaporation was found to release a significant amount of less oxidized oxygenated OA from air masses transported from polluted regions. The distinct decrease in OA / ΔCO with the increase in O / C during the cloud evaporative period further demonstrates that OA remaining in cloud droplets is generally in a moderate oxidation state. Moreover, organic nitrates were also estimated and showed a higher contribution to the total nitrate during the cloudy period (27 %) than during the evaporative period (3 %). Overall, our results demonstrate the importance of SOA and the influences of cloud processes in regional mountain areas in southeastern China.

The radiative forcing of black carbon (BC) depends strongly on its mixing state in different chemical environments. Here we analyzed the chemical composition and mixing state of BC-containing particles by using a single-particle aerosol mass spectrometer and investigated their impact on light absorption enhancement (Eabs) at an urban (Beijing) and a rural site (Gucheng) in the North China Plain. While the BC was dominantly mixed with organic carbon (OC), nitrate, and sulfate at both the urban and rural sites, the rural site showed a much higher fraction of BC coated with OC and nitrate (36 % vs. 15 %–20 %). Moreover, the BC mixing state evolved significantly as a function of relative humidity (RH), with largely increased coatings of OC–nitrate and nitrate at high RH levels. By linking with an organic aerosol (OA) composition, we found that the OC coated on BC comprised dominantly secondary OA in Beijing, while primary and secondary OA were similarly important in Gucheng. Furthermore, Eabs was highly dependent on secondary inorganic aerosol coated on BC at both sites, while the coated primary OC also resulted in an Eabs of ∼ 1.2 for relatively fresh BC particles at the rural site. A positive matrix factorization analysis was performed to quantify the impact of different mixing states on Eabs. Our results showed a small Eabs (1.06–1.11) for BC particles from fresh primary emissions, while the Eabs increased significantly above 1.3 when BC was aged rapidly with increased coatings of OC–nitrate or nitrate; it can reach above 1.4 as sulfate was involved in BC aging.

Brown carbon (BrC) aerosols exert vital impacts on climate change and atmospheric photochemistry due to their light absorption in the wavelength range from near-ultraviolet (UV) to visible light. However, the optical properties and formation mechanisms of ambient BrC remain poorly understood, limiting the estimation of their radiative forcing. In the present study, fine particles (PM2.5) were collected during 2016–2017 on a day/night basis over urban Tianjin, a megacity in northern China. Light absorption and fluorescence properties of water extracts of PM2.5 were investigated to obtain seasonal and diurnal patterns of atmospheric water-soluble BrC. There were obvious seasonal, but no evident diurnal, variations in the light absorption properties of BrC. In winter, BrC showed much stronger light-absorbing ability, with a mass absorption efficiency at 365 nm (MAE365) in winter (1.54±0.33 m2 gC−1) that was 1.8 times larger than MAE365 in summer (0.84±0.22 m2 gC−1). Direct radiative effects by BrC absorption relative to black carbon in the UV range were 54.3±16.9 % and 44.6±13.9 % in winter and summer, respectively. In addition, five fluorescent components in BrC, including three humic-like fluorophores and two protein-like fluorophores were identified with excitation–emission matrix fluorescence spectrometry and parallel factor (PARAFAC) analysis. The less oxygenated components contributed more to winter and nighttime samples, while more oxygenated components increased in summer and daytime samples. The higher humification index (HIX), together with lower biological index (BIX) and fluorescence index (FI), suggests that the chemical compositions of BrC were associated with a high aromaticity degree in summer and daytime due to photobleaching. Fluorescent properties indicate that wintertime BrC were predominantly affected by primary emissions and fresh secondary organic aerosol (SOA), while summer ones were more influenced by aging processes. Results of source apportionments using organic molecular compositions of the same set of aerosols reveal that fossil fuel combustion and aging processes, primary bioaerosol emission, biomass burning, and biogenic and anthropogenic SOA formation were the main sources of BrC. Biomass burning contributed much more to BrC in winter and at nighttime, while biogenic SOA contributed more in summer and during the daytime. In particular, our study highlights that primary bioaerosol emission is an important source of BrC in urban Tianjin in summer.

The variability of the mixing state of refractory black carbon aerosol (rBC) and the corresponding complicated light absorption capacity imposes great uncertainty for its climate forcing assessment. In this study, field observations using a single-particle soot photometer (SP2) were conducted to investigate the mixing state of rBC under different meteorological conditions at a rural site on the North China Plain. The results showed that the hourly mass concentration of rBC during the observation periods was 2.6±1.5 µg m−3 on average, with a moderate increase (3.1±0.9) during fog episodes. The mass-equivalent size distribution of rBC exhibited an approximately lognormal distribution with a mass median diameter (MMD) of 213 nm. We found that the count median diameter (CMD) of rBC particles during snowfall episodes was larger than that before snowfall, and the number of rBC particles with Dc nm were reduced by 28.4 % after snow. This may indicate that rBC-containing particles with small core sizes (Dc) were much more effectively removed by snow with light snow intensity (0.23 mm h−1). Based on the Mie scattering theory simulation, the relative and absolute coating thicknesses of rBC-containing particles were estimated to be ∼1.6 and ∼52 nm for the rBC core with a mass-equivalent diameter (Dc) of 170 to 190 nm, respectively, which indicates that most of the rBC-containing particles were thinly coated. Furthermore, a moderate light absorption enhancement (Eabs=1.3) and relatively low absorption cross section (MAC = 5.5 m2 g−1) at 880 nm were observed at the Gucheng (GC) site in winter compared with other typical rural sites. The relationship between the microphysical properties of rBC and meteorological conditions was also studied. Relatively warm and high-RH environments (RH>50 %, -4∘C

Understanding the global distribution of atmospheric black carbon (BC) is essential for unveiling its climatic effect. However, there are still large uncertainties regarding the simulation of BC transport due to inadequate information about the removal process. We accessed the wet removal rate of BC in East Asia based on long-term measurements over the 2010–2016 period at three representative background sites (Baengnyeong and Gosan in South Korea and Noto in Japan). The average wet removal rate, represented by transport efficiency (TE), i.e., the fraction of undeposited BC particles during transport, was estimated to be 0.73 in East Asia from 2010 to 2016. According to the relationship between accumulated precipitation along trajectory and TE, the wet removal efficiency was lower in East and North China but higher in South Korea and Japan, implying the importance of the aging process and frequency of exposure to below- and in-cloud scavenging conditions during air mass transport. Moreover, the wet scavenging in winter and summer showed the highest and lowest efficiency, respectively, although the lowest removal efficiency in summer was primarily associated with a reduced BC aging process because the in-cloud scavenging condition was dominant. The average half-life and e-folding lifetime of BC were 2.8 and 7.1 d, respectively, which is similar to previous studies, but those values differed according to the geographical location and meteorological conditions of each site. Next, by comparing TE from the FLEXible PARTicle (FLEXPART) Lagrangian transport model (version 10.4), we diagnosed the scavenging coefficients (s−1) of the below- and in-cloud scavenging scheme implemented in FLEXPART. The overall median TE from FLEXPART (0.91) was overestimated compared to the measured value, implying the underestimation of wet scavenging coefficients in the model simulation. The median of the measured below-cloud scavenging coefficient showed a lower value than that calculated according to FLEXPART scheme by a factor of 1.7. On the other hand, the overall median of the calculated in-cloud scavenging coefficients from the FLEXPART scheme was highly underestimated by 1 order of magnitude, compared to the measured value. From an analysis of artificial neural networks, the convective available potential energy, which is well known as an indicator of vertical instability, should be considered in the in-cloud scavenging process to improve the representative regional difference in BC wet scavenging over East Asia. For the first time, this study suggests an effective and straightforward evaluation method for wet scavenging schemes (both below and in cloud), by introducing TE along with excluding effects from the inaccurate emission inventories.

Marine aerosol samples collected from the South China Sea (SCS) to the eastern Indian Ocean (EIO) during a cruise from 10 March to 26 April 2015 were studied for diacids and related compounds. In view of air mass backward trajectories, source regions, and geographical features, the cruise area was categorized into the South China Sea (SCS), the eastern Indian Ocean off the coast of western Indonesia (EIO-WI), the EIO off the coast of Sri Lanka (EIO-SL), Malacca, and the Sri Lanka docking point (SLDP). Total concentrations of diacids, oxoacids, and α-dicarbonyls were high at the SLDP, followed by the SCS and Malacca, and they were the low in the EIO-WI. In this study, oxalic acid (C2) was the dominant diacid during the cruise, followed by malonic acid (C3) in the SCS, EIO-WI, EIO-SL, and Malacca, and succinic acid (C4) was relatively more abundant than C3 diacid at the SLDP. Except for SLDP, C3∕C4 mass ratios were always greater than 1, and no significant difference was observed during the cruise. The C2∕C4 and C2∕total diacid ratios also showed similar trends. The average mass ratios of adipic acid (C6) to azelaic acid (C9) were less than unity except for in the EIO-WI; the mass ratios of phthalic acid (Ph) to azelaic acid (C9) were less than 2 except for in the SCS. The concentrations of diacids were higher when the air masses originated from terrestrial regions than when they originated from remote oceanic regions. Based on the molecular distributions of organic acids, the mass ratios, and the linear correlations of selected compounds in each area, we found that the oxidation of biogenic volatile organic compounds (BVOCs) released from the ocean surface and subsequent in situ photochemical oxidation was the main contributor to diacids, oxocarboxylic acids, and α-dicarbonyls from the SCS to the EIO. In addition, the continental outflow, which is enriched in anthropogenic VOCs and their aged products, influenced the organic aerosol loading, particularly over the SCS. Emissions from Sri Lanka terrestrial vegetation as well as fossil fuel combustion and subsequent photochemical oxidation also played a prominent role in controlling the organic aerosol loading and the molecular distribution of diacids and related compounds at the SLDP.

Black carbon aerosols play an important role in climate change because they directly absorb solar radiation. In this study, the mixing state of refractory black carbon (rBC) at an urban site in Beijing in the early summer of 2018 was studied with a single-particle soot photometer (SP2) as well as a tandem observation system with a centrifugal particle mass analyzer (CPMA) and a differential mobility analyzer (DMA). The results demonstrated that the mass-equivalent size distribution of rBC exhibited an approximately lognormal distribution with a mass median diameter (MMD) of 171 nm. When the site experienced prevailing southerly winds, the MMD of rBC increased notably, by 19 %. During the observational period, the ratio of the diameter of rBC-containing particles (Dp) to the rBC core (Dc) was 1.20 on average for Dc=180 nm, indicating that the majority of rBC particles were thinly coated. The Dp∕Dc value exhibited a clear diurnal pattern, with a maximum at 14:00 LST and a Dp growth rate of 2.3 nm h−1; higher Ox conditions increased the coating growth rate. The microphysical properties of rBC were also studied. Bare rBC particles were mostly found in fractal structures with a mass fractal dimensions (Dfm) of 2.35, with limited variation during both clean and polluted periods. The morphology of rBC changed with coating thickness increasing. When the mass ratio of nonrefractory matter to rBC (MR) was MR>6, at which point the measured scattering cross section of rBC-containing particles was consistent with that based on the Mie-scattering simulation. We found that only 28 % of the rBC-containing particles were in core–shell structures with a particle mass of 10 fg in the clean period but that proportion increased considerably, to 45 %, in the polluted period. Due to the morphology change, the absorption enhancement (Eabs) was 12 % lower than that predicted for core–shell structures.

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.

Aerosol composition and sources have been extensively studied in developed regions in China. However, aerosol chemistry in coastal regions of eastern China with high industrial emissions remains poorly characterized. Here we present a comprehensive characterization of aerosol composition and sources near two large steel plants in a coastal city in Shandong in fall and spring using a PM2.5 time-of-flight aerosol chemical speciation monitor. The average (±1σ) mass concentration of PM2.5 in spring 2019 (54±44 µg m−3) was approximately twice that (26±23 µg m−3) in fall 2018. Aerosol composition was substantially different between the two seasons. While organics accounted for ∼30 % of the total PM2.5 mass in both seasons, sulfate showed a considerable decrease from 28 % in September to 16 % in March, which was associated with a large increase in nitrate contribution from 17 % to 32 %. Positive matrix factorization analysis showed that secondary organic aerosol (SOA) dominated the total OA in both seasons, accounting on average for 92 % and 86 %, respectively, while the contribution of traffic-related hydrocarbon-like OA was comparable (8 %–9 %). During this study, we observed significant impacts of steel plant emissions on aerosol chemistry nearby. The results showed that aerosol particles emitted from the steel plants were overwhelmingly dominated by ammonium sulfate and/or ammonium bisulfate with the peak concentration reaching as high as 224 µg m−3. Further analysis showed similar mass ratios for NOx∕CO (0.014) and NOx∕SO2 (1.24) from the two different steel plants, which were largely different from those during periods in the absence of industrial plumes. Bivariate polar plot analysis also supported the dominant source region of ammonium sulfate, CO, and SO2 from the southwest steel plants. Our results might have significant implications for better quantification of industrial emissions using ammonium sulfate and the ratios of gaseous species as tracers in industrial regions and nearby in the future.

In order to better understand the molecular composition and sources of organic aerosols in Tianjin, a coastal megacity in North China, ambient fine aerosol (PM2.5) samples were collected on a day/night basis from November to December 2016 and from May to June 2017. The organic molecular composition of PM2.5 components, including aliphatic lipids (n-alkanes, fatty acids, and fatty alcohols), sugar compounds, and photooxidation products from isoprene, monoterpene, β-caryophyllene, naphthalene, and toluene, was analysed using gas chromatography–mass spectrometry. Fatty acids, fatty alcohols, and saccharides were identified as the most abundant organic compound classes among all of the tracers detected in this study during both seasons. High concentrations of most organics at night in winter may be attributed to intensive residential activities such as house heating as well as the low nocturnal boundary layer height. Based on tracer methods, the contributions of the sum of primary and secondary organic carbon (POC and SOC respectively) to aerosol organic carbon (OC) were 24.8 % (daytime) and 27.6 % (night-time) in winter and 38.9 % (daytime) and 32.5 % (night-time) in summer. In detail, POC derived from fungal spores, plant debris, and biomass burning accounted for 2.78 %–31.6 % (12.4 %; please note that values displayed in parentheses in the following are average values) of OC during the daytime and 4.72 %–45.9 % (16.3 %) at night in winter, and 1.28 %–9.89 % (5.24 %) during the daytime and 2.08 %–47.2 % (10.6 %) at night in summer. Biomass-burning-derived OC was the predominant source of POC in this study, especially at night (16.0±6.88 % in winter and 9.62±8.73 % in summer). Biogenic SOC from isoprene, α-∕β-pinene, and β-caryophyllene exhibited obvious seasonal and diurnal patterns, contributing 2.23±1.27 % (2.30±1.35 % during the daytime and 2.18±1.19 % at night) and 8.60±4.02 % (8.98±3.67 % and 8.21±4.39 %) to OC in winter and summer respectively. Isoprene and α-∕β-pinene SOC were obviously elevated in summer, especially during the daytime, mainly due to strong photooxidation. Anthropogenic SOC from toluene and naphthalene oxidation showed higher contributions to OC in summer (21.0±18.5 %) than in winter (9.58±3.68 %). In summer, toluene SOC was the dominant contributor to aerosol OC, and biomass burning OC also accounted for a high contribution to OC, especially at night-time; this indicates that land/sea breezes also play an important role in the aerosol chemistry of the coastal city of Tianjin in North China.

The black carbon (BC) and carbon monoxide (CO) emission ratios were estimated and compiled from long-term, harmonized observations of the ΔBC∕ΔCO ratios under conditions unaffected by wet deposition at four sites in East Asia, including two sites in South Korea (Baengnyeong and Gosan) and two sites in Japan (Noto and Fukuoka). Extended spatio-temporal coverage enabled estimation of the full seasonality and elucidation of the emission ratio in North Korea for the first time. The estimated ratios were used to validate the Regional Emission inventory in ASia (REAS) version 2.1 based on six study domains (“East China”, “North China”, “Northeast China”, South Korea, North Korea, and Japan). We found that the ΔBC∕ΔCO ratios from four sites converged into a narrow range (6.2–7.9 ng m−3 ppb−1), suggesting consistency in the results from independent observations and similarity in source profiles over the regions. The BC∕CO ratios from the REAS emission inventory (7.7 ng m−3 ppb−1 for East China – 23.2 ng m−3 ppb−1 for South Korea) were overestimated by factors of 1.1 for East China to 3.0 for South Korea, whereas the ratio for North Korea (3.7 ng m−3 ppb−1 from REAS) was underestimated by a factor of 2.0, most likely due to inaccurate emissions from the road transportation sector. Seasonal variation in the BC∕CO ratio from REAS was found to be the highest in winter (China and North Korea) or summer (South Korea and Japan), whereas the measured ΔBC∕ΔCO ratio was the highest in spring in all source regions, indicating the need for further characterization of the seasonality when creating a bottom-up emission inventory. At levels of administrative districts, overestimation in Seoul, the southwestern regions of South Korea, and Northeast China was noticeable, and underestimation was mainly observed in the western regions in North Korea, including Pyongyang. These diagnoses are useful for identifying regions where revisions in the inventory are necessary, providing guidance for the refinement of BC and CO emission rate estimates over East Asia.

Aerosols from biomass burning (BB) emissions are poorly constrained in global and regional models, resulting in a high level of uncertainty in understanding their impacts. In this study, we compared six BB aerosol emission datasets for 2008 globally as well as in 14 regions. The six BB emission datasets are (1) GFED3.1 (Global Fire Emissions Database version 3.1), (2) GFED4s (GFED version 4 with small fires), (3) FINN1.5 (FIre INventory from NCAR version 1.5), (4) GFAS1.2 (Global Fire Assimilation System version 1.2), (5) FEER1.0 (Fire Energetics and Emissions Research version 1.0), and (6) QFED2.4 (Quick Fire Emissions Dataset version 2.4). The global total emission amounts from these six BB emission datasets differed by a factor of 3.8, ranging from 13.76 to 51.93 Tg for organic carbon and from 1.65 to 5.54 Tg for black carbon. In most of the regions, QFED2.4 and FEER1.0, which are based on satellite observations of fire radiative power (FRP) and constrained by aerosol optical depth (AOD) data from the Moderate Resolution Imaging Spectroradiometer (MODIS), yielded higher BB aerosol emissions than the rest by a factor of 2–4. By comparison, the BB aerosol emissions estimated from GFED4s and GFED3.1, which are based on satellite burned-area data, without AOD constraints, were at the low end of the range. In order to examine the sensitivity of model-simulated AOD to the different BB emission datasets, we ingested these six BB emission datasets separately into the same global model, the NASA Goddard Earth Observing System (GEOS) model, and compared the simulated AOD with observed AOD from the AErosol RObotic NETwork (AERONET) and the Multiangle Imaging SpectroRadiometer (MISR) in the 14 regions during 2008. In Southern Hemisphere Africa (SHAF) and South America (SHSA), where aerosols tend to be clearly dominated by smoke in September, the simulated AOD values were underestimated in almost all experiments compared to MISR, except for the QFED2.4 run in SHSA. The model-simulated AOD values based on FEER1.0 and QFED2.4 were the closest to the corresponding AERONET data, being, respectively, about 73 % and 100 % of the AERONET observed AOD at Alta Floresta in SHSA and about 49 % and 46 % at Mongu in SHAF. The simulated AOD based on the other four BB emission datasets accounted for only ∼50 % of the AERONET AOD at Alta Floresta and ∼20 % at Mongu. Overall, during the biomass burning peak seasons, at most of the selected AERONET sites in each region, the AOD values simulated with QFED2.4 were the highest and closest to AERONET and MISR observations, followed closely by FEER1.0. However, the QFED2.4 run tends to overestimate AOD in the region of SHSA, and the QFED2.4 BB emission dataset is tuned with the GEOS model. In contrast, the FEER1.0 BB emission dataset is derived in a more model-independent fashion and is more physically based since its emission coefficients are independently derived at each grid box. Therefore, we recommend the FEER1.0 BB emission dataset for aerosol-focused hindcast experiments in the two biomass-burning-dominated regions in the Southern Hemisphere, SHAF, and SHSA (as well as in other regions but with lower confidence). The differences between these six BB emission datasets are attributable to the approaches and input data used to derive BB emissions, such as whether AOD from satellite observations is used as a constraint, whether the approaches to parameterize the fire activities are based on burned area, FRP, or active fire count, and which set of emission factors is chosen.

The effective density (ρeff) of refractory black carbon (rBC) is a key parameter relevant to its mixing state that imposes great uncertainty in evaluating the direct radiation forcing effect. In this study, a tandem differential mobility analyzer–centrifugal particle analyzer–single-particle soot photometer (DMA–CPMA–SP2) system was used to investigate the relationship between the effective density (ρeff) and the mixing state of rBC particles during the winter of 2018 in the Beijing megacity. During the experiment, aerosols with a known mobility diameter (Dmob) and known ρeff values (0.8, 1.0, 1.2, 1.4, 1.6, and 1.8 g cm−3) were precisely selected and measured by the SP2 to obtain their corresponding mixing states. The results showed that the ρeff well represented the morphological variation in rBC-containing particles. The rBC-containing particles changed from an irregular structure to a compact spherical structure with the increase in ρeff. A ρeff value of 1.4 g cm−3 was the morphological transition point. The morphology and ρeff value of the rBC-containing particles were intrinsically related to the mass ratio of non-refractory matter to rBC (MR). As the ρeff values of the rBC-containing particles increased from 0.8 to 1.8 g cm−3, the MR of the rBC-containing particles significantly increased from 2 up to 6–8, indicating that atmospheric aging processes were likely to lead to the reconstruction of more compact and regular particle shapes. During the observation period, the ρeff of the majority of rBC-containing particles was smaller than the morphology transition point independent of the pollution conditions. This suggested that the major rBC-containing particles did not have a spherical structure. Simulation based on an aggregate model considering the morphological information of the particles demonstrated that absorption enhancement of rBC-containing particles could be overestimated by ∼ 17 % by using a core–shell model. This study highlights the strong dependence of the morphology of ambient rBC-containing particles on ρeff and will be helpful for elucidating the microphysical characteristics of rBC and reducing uncertainty in the evaluation of rBC climate effects and health risks.

Wet scavenging is one of the most efficient processes for removing aerosols from the atmosphere. This process is not well constrained in chemical transport models (CTMs) due to a paucity of localized parameterization regarding the below-cloud wet scavenging coefficient (BWSC). Here we conducted field measurements of the BWSC during the Atmospheric Pollution and Human Health Beijing (APHH-Beijing) campaign of 2016. Notably, the observed BWSC values based on the updated aerosol mass balance agree well with another estimation technique, and they fall in a range of 10−5 s−1. The measurement in this winter campaign, combined with that in summer of 2014, supported an exponential power distribution of BWSCs with rainfall intensity. The observed parameters were also compared with both the theoretical calculations and modeling results. We found that the theoretical estimations can effectively characterize the observed BWSCs of aerosols with sizes smaller than 0.2 µm and larger than 2.5 µm. However, the theoretical estimations were an order of magnitude lower than observed BWSCs within 0.2–2.5 µm, a domain size range of urban aerosols. Such an underestimation of BWSC through a theoretical method has been confirmed not only in APHH-Beijing campaign but also in all the rainfall events in summer of 2014. Since the model calculations usually originated from the theoretical estimations with simplified scheme, the significantly lower BWSC could well explain the underprediction of wet depositions in polluted regions as reported by the Model Inter-Comparison Study for Asia (MICS-Asia) and the global assessment of the Task Force on Hemispheric Transport of Atmospheric Pollutants (TF-HTAP). The findings highlighted that the wet deposition module in the CTMs requires improvement based on field measurement estimation to construct a more reasonable simulation scheme for BWSC, especially in polluted regions.

Constraints from ozone (O3) observations over oceans are needed in addition to those from terrestrial regions to fully understand global tropospheric chemistry and its impact on the climate. Here, we provide a large data set of ozone and carbon monoxide (CO) levels observed (for 11 666 and 10 681 h, respectively) over oceans. The data set is derived from observations made during 24 research cruise legs of R/V Mirai during 2012 to 2017, in the Southern, Indian, Pacific, and Arctic oceans, covering the region from 67∘ S to 75∘ N. The data are suitable for critical evaluation of the over-ocean distribution of ozone derived from global atmospheric chemistry models. We first give an overview of the statistics in the data set and highlight key features in terms of geographical distribution and air mass type. We then use the data set to evaluate ozone mixing ratio fields from the tropospheric chemistry reanalysis version 2 (TCR-2), produced by assimilating a suite of satellite observations of multiple species into a global atmospheric chemistry model, namely CHASER. For long-range transport of polluted air masses from continents to the oceans, during which the effects of forest fires and fossil fuel combustion were recognized, TCR-2 gave an excellent performance in reproducing the observed temporal variations and photochemical buildup of O3 when assessed from ΔO3∕ΔCO ratios. For clean marine conditions with low and stable CO mixing ratios, two focused analyses were performed. The first was in the Arctic (> 70∘ N) in September every year from 2013 to 2016; TCR-2 underpredicted O3 levels by 6.7 ppbv (21 %) on average. The observed vertical profiles from O3 soundings from R/V Mirai during September 2014 had less steep vertical gradients at low altitudes (> 850 hPa) than those obtained by TCR-2. This suggests the possibility of a more efficient descent of the O3-rich air from above than assumed in the models. For TCR-2 (CHASER), dry deposition on the Arctic ocean surface might also have been overestimated. In the second analysis, over the western Pacific equatorial region (125–165∘ E, 10∘ S to 25∘ N), the observed O3 level more frequently decreased to less than 10 ppbv in comparison to that obtained with TCR-2 and also those obtained in most of the Atmospheric Chemistry Climate Model Intercomparison Project (ACCMIP) model runs for the decade from 2000. These results imply loss processes that are unaccounted for in the models. We found that the model's positive bias positively correlated with the daytime residence times of air masses over a particular grid, namely 165–180∘ E and 15–30∘ N; an additional loss rate of 0.25 ppbv h−1 in the grid best explained the gap. Halogen chemistry, which is commonly omitted from currently used models, might be active in this region and could have contributed to additional losses. Our open data set covering wide ocean regions is complementary to the Tropospheric Ozone Assessment Report data set, which basically comprises ground-based observations and enables a fully global study of the behavior of O3.

Depolarization ratio (δ) of backscattered light is an applicable parameter for distinguishing the sphericity of particles in real time, which has been widely adopted by ground-based lidar observation systems. In this study, δ values of particles and chemical compositions in both PM2.5 (aerodynamic diameter less than 2.5 µm) and PM10 (aerodynamic diameter less than 10 µm) were concurrently measured on the basis of a bench-top optical particle counter with a polarization detection module (POPC) and a continuous dichotomous aerosol chemical speciation analyzer (ACSA-14) from November 2016 to February 2017 at an urban site in Beijing megacity. In general, measured δ values depended on both size and sphericity of the particles. During the observation period, mass concentrations of NO3- in PM2.5 (fNO3) were about an order of magnitude higher than that in PM2.5−10 (cNO3) with a mean fNO3∕cNO3 ratio of 14±10. A relatively low fNO3∕cNO3 ratio (∼5) was also observed under higher relative humidity conditions, mostly due to heterogeneous processes and particles in the coarse mode. We found that δ values of ambient particles in both PM2.5 and PM2.5−10 obviously decreased as mass concentration of water-soluble species increased at unfavorable meteorological conditions. This indicated that the morphology of particles was changed as a result of water-absorbing processes. The particles with optical size (Dp) of Dp = 5 µm were used to represent mineral dust particles, and its δ values (δDp=5) decreased by 50 % as the mass fraction of cNO3 increased from 2 % to 8 % and ambient relative humidity increased up to 80 %, suggesting that mineral dust particles were likely to be spherical during humid pollution episodes. During the observation, relative humidity inside the POPC measuring chamber was stable at 34±2 %, lower than the ambient condition. Its influence on the morphology was estimated to be limited and did not change our major conclusion. This study highlights the evident alteration of non-sphericity of mineral dust particles during their transport owing to a synergistic effect of both pollutant coatings and hygroscopic processes, which plays an important role in the evaluation of its environmental effect.

East Asia is suffering from severe air pollution problems due to intensive anthropogenic emissions and natural mineral dust aerosols. During transport, the aerosol particles undergo complex mixing processes, resulting in great impacts on regional air quality, human health and climate. In this study, we conducted a long-term observation using an optical particle counter equipped with a polarization detection module (POPC) at an urban site in Beijing. Mass concentrations of both PM2.5 and PM10 estimated from POPC compared well with ground-based measurements. The results revealed that the observed depolarization ratio (δ, termed as the ratio of the intensity of the s-polarized signal to the intensity of the 120∘ backward scattering signal [s/(s+p)]) for aerosol particles in the fine mode was generally much lower in summer than that in spring as a result of predominance of different aerosol types. Mineral dust particles in the coarse mode normally had a large δ value (0.3±0.05) owing to their nonspherical shape; however, particles in the fine mode mostly had water-soluble compositions, which led to an apparent decrease of their δ values in particular high relative humidity (RH) conditions. Because the observation site was subject to the impact of frequent dust events in spring, the δ value of particle at 1 µm was almost twice as high as that (0.07±0.01) in summer. Based on size-resolved δ values, anthropogenic pollutants, mineral dust and polluted mineral dust particles and their contribution to local air quality could be well distinguished. About 26.7 % of substandard days (daily averaged PM2.5 concentration larger than 75 µg m−3) in Beijing featured high atmospheric loading of coarse-mode particles in winter and springtime. In particular, during severe pollution episodes in winter, the δ values of coarse-mode particles decreased by 13 %, which implies a high possibility of dust-related heterogeneous processes in pollution formation. During dust events, δ values of particles with optical size (Dp) of 5 µm evidently decreased, with an increase of the PM2.5 ∕ PM10 ratio as well as RH, indicating the morphological changes of mineral dust. This study confirmed that high RH tends to promote water absorption processes on the dust surface as well as the coating of soluble compounds, and suggested that remote sensing techniques for aerosols may underestimate the impact of dust particles due to the complex mixing of dust and anthropogenic particles in urban areas, and the interaction between dust particles and pollutants should be considered well by the optical model.

Ambient air pollution from ozone and fine particulate matter is associated with premature mortality. As emissions from one continent influence air quality over others, changes in emissions can also influence human health on other continents. We estimate global air-pollution-related premature mortality from exposure to PM2.5 and ozone and the avoided deaths due to 20 % anthropogenic emission reductions from six source regions, North America (NAM), Europe (EUR), South Asia (SAS), East Asia (EAS), Russia–Belarus–Ukraine (RBU), and the Middle East (MDE), three global emission sectors, power and industry (PIN), ground transportation (TRN), and residential (RES), and one global domain (GLO), using an ensemble of global chemical transport model simulations coordinated by the second phase of the Task Force on Hemispheric Transport of Air Pollutants (TF HTAP2), and epidemiologically derived concentration response functions. We build on results from previous studies of TF HTAP by using improved atmospheric models driven by new estimates of 2010 anthropogenic emissions (excluding methane), with more source and receptor regions, new consideration of source sector impacts, and new epidemiological mortality functions. We estimate 290 000 (95 % confidence interval (CI): 30 000, 600 000) premature O3-related deaths and 2.8 million (0.5 million, 4.6 million) PM2.5-related premature deaths globally for the baseline year 2010. While 20 % emission reductions from one region generally lead to more avoided deaths within the source region than outside, reducing emissions from MDE and RBU can avoid more O3-related deaths outside of these regions than within, and reducing MDE emissions also avoids more PM2.5-related deaths outside of MDE than within. Our findings that most avoided O3-related deaths from emission reductions in NAM and EUR occur outside of those regions contrast with those of previous studies, while estimates of PM2.5-related deaths from NAM, EUR, SAS, and EAS emission reductions agree well. In addition, EUR, MDE, and RBU have more avoided O3-related deaths from reducing foreign emissions than from domestic reductions. For six regional emission reductions, the total avoided extra-regional mortality is estimated as 6000 (−3400, 15 500) deaths per year and 25 100 (8200, 35 800) deaths per year through changes in O3 and PM2.5, respectively. Interregional transport of air pollutants leads to more deaths through changes in PM2.5 than in O3, even though O3 is transported more on interregional scales, since PM2.5 has a stronger influence on mortality. For NAM and EUR, our estimates of avoided mortality from regional and extra-regional emission reductions are comparable to those estimated by regional models for these same experiments. In sectoral emission reductions, TRN emissions account for the greatest fraction (26–53 % of global emission reduction) of O3-related premature deaths in most regions, in agreement with previous studies, except for EAS (58 %) and RBU (38 %) where PIN emissions dominate. In contrast, PIN emission reductions have the greatest fraction (38–78 % of global emission reduction) of PM2.5-related deaths in most regions, except for SAS (45 %) where RES emission dominates, which differs with previous studies in which RES emissions dominate global health impacts. The spread of air pollutant concentration changes across models contributes most to the overall uncertainty in estimated avoided deaths, highlighting the uncertainty in results based on a single model. Despite uncertainties, the health benefits of reduced intercontinental air pollution transport suggest that international cooperation may be desirable to mitigate pollution transported over long distances.

The emission characteristics of refractory black carbon (rBC) from biomass burning are essential information for numerical simulations of regional pollution and climate effects. We conducted combustion experiments in the laboratory to investigate the emission ratio and mixing state of rBC from the burning of wheat straw and rapeseed plants, which are the main crops cultivated in the Yangtze River Delta region of China. A single particle soot photometer (SP2) was used to measure rBC-containing particles at high temporal resolution and with high accuracy. The combustion state of each burning case was indicated by the modified combustion efficiency (MCE), which is calculated using the integrated enhancement of carbon dioxide and carbon monoxide concentrations relative to their background values. The mass size distribution of the rBC particles showed a lognormal shape with a mode mass equivalent diameter (MED) of 189 nm (ranging from 152 to 215 nm), assuming an rBC density of 1.8 g cm−3. rBC particles less than 80 nm in size (the lower detection limit of the SP2) accounted for ∼ 5 % of the total rBC mass, on average. The emission ratios, which are expressed as ΔrBC ∕ ΔCO (Δ indicates the difference between the observed and background values), displayed a significant positive correlation with the MCE values and varied between 1.8 and 34 ng m−3 ppbv−1. Multi-peak fitting analysis of the delay time (Δt, or the time of occurrence of the scattering peak minus that of the incandescence peak) distribution showed that rBC-containing particles with rBC MED = 200 ± 10 nm displayed two peaks at Δt = 1.7 µs and Δt = 3.2 µs, which could be attributed to the contributions from both flaming and smoldering combustion in each burning case. Both the Δt values and the shell / core ratios of the rBC-containing particles clearly increased as the MCE decreased from 0.98 (smoldering-dominant combustion) to 0.86 (flaming-dominant combustion), implying the great importance of the rapid condensation of semi-volatile organics. This laboratory study found that the mixing state of rBC particles from biomass burning strongly depends on its combustion processes, and overall MCE should be taken carefully into consideration while the climate effect of rBC particles from open biomass burning is simulated.

An assessment of global particulate nitrate and ammonium aerosol based on simulations from nine models participating in the Aerosol Comparisons between Observations and Models (AeroCom) phase III study is presented. A budget analysis was conducted to understand the typical magnitude, distribution, and diversity of the aerosols and their precursors among the models. To gain confidence regarding model performance, the model results were evaluated with various observations globally, including ground station measurements over North America, Europe, and east Asia for tracer concentrations and dry and wet depositions, as well as with aircraft measurements in the Northern Hemisphere mid-to-high latitudes for tracer vertical distributions. Given the unique chemical and physical features of the nitrate occurrence, we further investigated the similarity and differentiation among the models by examining (1) the pH-dependent NH3 wet deposition; (2) the nitrate formation via heterogeneous chemistry on the surface of dust and sea salt particles or thermodynamic equilibrium calculation including dust and sea salt ions; and (3) the nitrate coarse-mode fraction (i.e., coarse/total). It is found that HNO3, which is simulated explicitly based on full O3-HOx-NOx-aerosol chemistry by all models, differs by up to a factor of 9 among the models in its global tropospheric burden. This partially contributes to a large difference in NO3−, whose atmospheric burden differs by up to a factor of 13. The atmospheric burdens of NH3 and NH4+ differ by 17 and 4, respectively. Analyses at the process level show that the large diversity in atmospheric burdens of NO3−, NH3, and NH4+ is also related to deposition processes. Wet deposition seems to be the dominant process in determining the diversity in NH3 and NH4+ lifetimes. It is critical to correctly account for contributions of heterogeneous chemical production of nitrate on dust and sea salt, because this process overwhelmingly controls atmospheric nitrate production (typically > 80 %) and determines the coarse- and fine-mode distribution of nitrate aerosol.

We analyzed long-term fine- and coarse-mode synergetic observations of nitrate and related aerosols (SO42−, NO3−, NH4+, Na+, Ca2+) at Fukuoka (33.52° N, 130.47° E) from August 2014 to October 2015. A Goddard Earth Observing System chemical transport model (GEOS-Chem) including dust and sea salt acid uptake processes was used to assess the observed seasonal variation and the impact of long-range transport (LRT) from the Asian continent. For fine aerosols (fSO42−, fNO3−, and fNH4+), numerical results explained the seasonal changes, and a sensitivity analysis excluding Japanese domestic emissions clarified the LRT fraction at Fukuoka (85 % for fSO42−, 47 % for fNO3−, 73 % for fNH4+). Observational data confirmed that coarse NO3− (cNO3−) made up the largest proportion (i.e., 40–55 %) of the total nitrate (defined as the sum of fNO3−, cNO3−, and HNO3) during the winter, while HNO3 gas constituted approximately 40 % of the total nitrate in summer and fNO3− peaked during the winter. Large-scale dust–nitrate (mainly cNO3−) outflow from China to Fukuoka was confirmed during all dust events that occurred between January and June. The modeled cNO3− was in good agreement with observations between July and November (mainly coming from sea salt NO3−). During the winter, however, the model underestimated cNO3− levels compared to the observed levels. The reason for this underestimation was examined statistically using multiple regression analysis (MRA). We used cNa+, nss-cCa2+, and cNH4+ as independent variables to describe the observed cNO3− levels; these variables were considered representative of sea salt cNO3−, dust cNO3−, and cNO3− accompanied by cNH4+), respectively. The MRA results explained the observed seasonal changes in dust cNO3− and indicated that the dust–acid uptake scheme reproduced the observed dust–nitrate levels even in winter. The annual average contributions of each component were 43 % (sea salt cNO3−), 19 % (dust cNO3−), and 38 % (cNH4+ term). The MRA dust–cNO3− component had a high value during the dust season, and the sea salt component made a large contribution throughout the year. During the winter, cNH4+ term made a large contribution. The model did not include aerosol microphysical processes (such as condensation and coagulation between the fine anthropogenic aerosols NO3− and SO42− and coarse particles), and our results suggest that inclusion of aerosol microphysical processes is critical when studying observed cNO3− formation, especially in winter.

Ground-based observation of the polarization properties of aerosol particles using a polarization optical particle counter (POPC) was made from 27 October 2013, to 31 December 2015, at a suburban site in the Kyushu area of Japan. We found that the depolarization ratio (DR, the fraction of s-polarized signal in the total backward light scattering signal) of aerosol particles showed prominent seasonal variability, with peaks in spring (0.21–0.23) and winter (0.19–0.23), and a minimum value (0.09–0.14) in summer. The aerosol compositions in both fine mode (aerodynamic diameter of particle, Dp Dp Dp > 1 µm) particles. Occurrence of substandard air quality days in Kyushu was closely related with mixed type (coexistence of anthropogenic pollutants and dust particles in the atmosphere), especially in winter and spring, indicating that dust events in the Asian continent played a key role in the cross-boundary transport of continental pollution. Backward trajectory analysis demonstrated that air masses originating from the western Pacific contained large amounts of spherical particles due to the influence of sea salt, especially in summer; however, for air masses from the Asian continent, the dependence of number fraction of spherical particles on air relative humidity was insignificant, indicating the predominance of less-hygroscopic substances (e.g., mineral dust), although the mass concentrations of anthropogenic pollutants were elevated.

Long-term (2009–2015) observations of atmospheric black carbon (BC) mass concentrations were performed using a continuous soot-monitoring system (COSMOS) at Fukue Island, western Japan, to provide information on wet removal rate constraints and the emission strengths of important source regions in East Asia (China and others). The annual average mass concentration was 0.36 µg m−3, with distinct seasonality; high concentrations were recorded during autumn, winter, and spring and were caused by Asian continental outflows, which reached Fukue Island in 6–46 h. The observed data were categorized into two classes, i.e., with and without a wet removal effect, using the accumulated precipitation along a backward trajectory (APT) for the last 3 days as an index. Statistical analysis of the observed ΔBC ∕ ΔCO ratios was performed to obtain information on the emission ratios (from data with zero APT only) and wet removal rates (including data with nonzero APTs). The estimated emission ratios (5.2–6.9 ng m−3 ppb−1) varied over the six air mass origin areas; the higher ratios for south-central East China (30–35° N) than for north-central East China (35–40° N) indicated the relative importance of domestic emissions and/or biomass burning sectors. The significantly higher BC ∕ CO emission ratios adopted in the bottom-up Regional Emission inventory in Asia (REAS) version 2 (8.3–23 ng m−3 ppb−1) over central East China and Korea needed to be reduced at least by factors of 1.3 and 2.8 for central East China and Korea, respectively, but the ratio for Japan was reasonable. The wintertime enhancement of the BC emission from China, predicted by REAS2, was verified for air masses from south-central East China but not for those from north-central East China. Wet removal of BC was clearly identified as a decrease in the ΔBC ∕ ΔCO ratio against APT. The transport efficiency (TE), defined as the ratio of the ΔBC ∕ ΔCO ratio with precipitation to that without precipitation, was fitted reasonably well by a stretched exponential decay curve against APT; a single set of fitting parameters was sufficient to represent the results for air masses originating from different areas. An accumulated precipitation of 25.5 ± 6.1 mm reduced the TE to 1∕e. BC-containing particles traveling to Fukue must have already been converted from hydrophobic to hydrophilic particles, because the behavior of TE against APT was similar to that of PM2.5, the major components of which are hydrophilic. Wet loss of BC greatly influenced interannual variations in the ΔBC ∕ ΔCO ratios and BC mass concentrations. This long-term data set will provide a benchmark for testing chemical transport/climate model simulations covering East Asia.

Open biomass burning (OBB) emits significant amounts of non-methane hydrocarbons (NMHCs), and the mixing of OBB with urban plumes could exacerbate regional ozone (O3) pollution. In the present study, an observational field campaign was performed in a rural area at the northern edge of the Yangtze River Delta region (YRDR) from 15 May to 24 June 2010, during intensive open burning of wheat residues. The net photochemical production rate of oxidant (Ox = O3 + NO2) at the site was evaluated based on a box model (Regional Atmospheric Chemical Mechanism, Version 2) constrained by real-time ambient measurements (e.g., O3, volatile organic compounds (VOCs), NOx (NO2 + NO), J values). Our results showed that both in situ photochemistry and direct transport from urban areas in the YRDR were responsible for the high Ox concentration at the site. During an OBB-impact case, net photochemical production of Ox in the daytime was pronounced, with a 6 h averaged Ox production rate of 13 ± 4 ppbv h−1 (maximum value of 21 ppbv h−1 at 12:00 CST). Photochemical Oxproduction changed from VOC-limited in the morning to NOx-limited in the afternoon due to the rapid photochemical consumption of NOx during the day. A combined analysis with positive matrix factorization demonstrated that O3 pollution in the rural area of the YRDR was largely affected by urban emission, and OBB-related emissions also contributed to in situ photochemical production, particularly in the afternoon. Our study suggested that a joint effort in reducing both NMHCs (e.g., aromatics) and NOx emissions in the urban area, as well as local OBB activities, may be effective in eliminating high-O3 pollution risk in the rural areas of the YRDR.

Atmospheric pollution over South Asia attracts special attention due to its effects on regional climate, water cycle and human health. These effects are potentially growing owing to rising trends of anthropogenic aerosol emissions. In this study, the spatio-temporal aerosol distributions over South Asia from seven global aerosol models are evaluated against aerosol retrievals from NASA satellite sensors and ground-based measurements for the period of 2000–2007. Overall, substantial underestimations of aerosol loading over South Asia are found systematically in most model simulations. Averaged over the entire South Asia, the annual mean aerosol optical depth (AOD) is underestimated by a range 15 to 44% across models compared to MISR (Multi-angle Imaging SpectroRadiometer), which is the lowest bound among various satellite AOD retrievals (from MISR, SeaWiFS (Sea-Viewing Wide Field-of-View Sensor), MODIS (Moderate Resolution Imaging Spectroradiometer) Aqua and Terra). In particular during the post-monsoon and wintertime periods (i.e., October–January), when agricultural waste burning and anthropogenic emissions dominate, models fail to capture AOD and aerosol absorption optical depth (AAOD) over the Indo–Gangetic Plain (IGP) compared to ground-based Aerosol Robotic Network (AERONET) sunphotometer measurements. The underestimations of aerosol loading in models generally occur in the lower troposphere (below 2 km) based on the comparisons of aerosol extinction profiles calculated by the models with those from Cloud–Aerosol Lidar with Orthogonal Polarization (CALIOP) data. Furthermore, surface concentrations of all aerosol components (sulfate, nitrate, organic aerosol (OA) and black carbon (BC)) from the models are found much lower than in situ measurements in winter. Several possible causes for these common problems of underestimating aerosols in models during the post-monsoon and wintertime periods are identified: the aerosol hygroscopic growth and formation of secondary inorganic aerosol are suppressed in the models because relative humidity (RH) is biased far too low in the boundary layer and thus foggy conditions are poorly represented in current models, the nitrate aerosol is either missing or inadequately accounted for, and emissions from agricultural waste burning and biofuel usage are too low in the emission inventories. These common problems and possible causes found in multiple models point out directions for future model improvements in this important region.

Aerosol variations and trends over different land and ocean regions from 1980 to 2009 are analyzed with the Goddard Chemistry Aerosol Radiation and Transport (GOCART) model and observations from multiple satellite sensors and available ground-based networks. Excluding time periods with large volcanic influence, aerosol optical depth (AOD) and surface concentration over polluted land regions generally vary with anthropogenic emissions, but the magnitude of this association can be dampened by the presence of natural aerosols, especially dust. Over the 30-year period in this study, the largest reduction in aerosol levels occurs over Europe, where AOD has decreased by 40–60% on average and surface sulfate concentrations have declined by a factor of up to 3–4. In contrast, East Asia and South Asia show AOD increases, but the relatively high level of dust aerosols in Asia reduces the correlation between AOD and pollutant emission trends. Over major dust source regions, model analysis indicates that the change of dust emissions over the Sahara and Sahel has been predominantly driven by the change of near-surface wind speed, but over Central Asia it has been largely influenced by the change of the surface wetness. The decreasing dust trend in the North African dust outflow region of the tropical North Atlantic and the receptor sites of Barbados and Miami is closely associated with an increase of the sea surface temperature in the North Atlantic. This temperature increase may drive the decrease of the wind velocity over North Africa, which reduces the dust emission, and the increase of precipitation over the tropical North Atlantic, which enhances dust removal during transport. Despite significant trends over some major continental source regions, the model-calculated global annual average AOD shows little change over land and ocean in the past three decades, because opposite trends in different land regions cancel each other out in the global average, and changes over large open oceans are negligible. This highlights the necessity for regional-scale assessment of aerosols and their climate impacts, as global-scale average values can obscure important regional changes.

We use the NASA GEOS-5 transport model with tagged tracers to investigate the contributions of different regional sources of CO and black carbon (BC) to their concentrations in the Western Arctic (i.e., 50–90° N and 190–320° E) in spring and summer 2008. The model is evaluated by comparing the results with airborne measurements of CO and BC from the NASA Arctic Research of the Composition of the Troposphere from Aircraft and Satellites (ARCTAS) field campaigns to demonstrate the strengths and limitations of our simulations. We also examine the reliability of tagged CO tracers in characterizing air mass origins using the measured fossil fuel tracer of dichloromethane and the biomass burning tracer of acetonitrile. Our tagged CO simulations suggest that most of the enhanced CO concentrations (above background level from CH4 production) observed during April originate from Asian anthropogenic emissions. Boreal biomass burning emissions and Asian anthropogenic emissions are of similar importance in July domain wise, although the biomass burning CO fraction is much larger in the area of the ARCTAS field experiments. The fraction of CO from Asian anthropogenic emissions is larger in spring than in summer. European sources make up no more than 10% of CO levels in the campaign domain during either period. Comparisons of CO concentrations along the flight tracks with regional averages from GEOS-5 show that the along-track measurements are representative of the concentrations within the large domain of the Western Arctic in April but not in July.

Photodegradation of secondary organic aerosol (SOA) prepared by ozone-initiated oxidation of D-limonene is studied with an action spectroscopy approach, which relies on detection of volatile photoproducts with chemical ionization mass-spectrometry as a function of the UV irradiation wavelength. Efficient photodegradation is observed for a broad range of ozone (0.1–300 ppm) and D-limonene (0.02–3 ppm) concentrations used in the preparation of SOA. The observed photoproducts are dominated by oxygenated C1-C3 compounds such as methanol, formic acid, acetaldehyde, acetic acid, and acetone. The irradiation wavelength dependence of the combined yield of the photoproducts closely tracks the absorption spectrum of the SOA material suggesting that photodegradation is not limited to the UV wavelengths. Kinetic simulations suggest that RO2+HO2/RO2 reactions represent the dominant route to photochemically active carbonyl and peroxide species in the limonene SOA prepared in these experiments. Similar photodegradation processes are likely to occur in realistic SOA produced by OH- or O3-initiated oxidation of biogenic volatile organic compounds in clean air.

Mixing state and density are two key parameters of aerosol particles affecting their impacts on radiative forcing and human health. Here a single-particle aerosol mass spectrometer in tandem with a differential mobility analyzer and an aerodynamic aerosol classifier was deployed during the Beijing 2022 Olympic Winter Games (OWG) to investigate the impacts of emission controls on particle mixing state and density. Our results show the dominance of carbonaceous particles comprising mainly total elemental carbon (Total-EC, 13.4 %), total organic carbon (Total-OC, 10.5 %) and Total-ECOC (47.1 %). Particularly, the particles containing organic carbon and sulfate were enhanced significantly during OWG, although those from primary emissions decreased. The composition of carbonaceous particles also changed significantly which was characterized by the decreases in EC mixed with nitrate and sulfate (EC-NS), EC mixed with potassium nitrate (KEC-N), and amine-containing particles and increase in ECOC mixed with nitrate and sulfate (ECOC-NS). This result indicates that emission controls during OWG reduced the mixing of EC with inorganic aerosol species and amines yet increased the mixing of EC with organic aerosol. The average effective density (ρeff) of aerosol particles (150–300 nm) was 1.15 g cm−3 during the non-Olympic Winter Games (nOWG), with higher values during OWG (1.26 g cm−3) due to the increase in secondary particle contribution. In addition, the ρeff of most particles increased with the increases in pollution levels and relative humidity, yet they varied differently for different types of particles, highlighting the impacts of aging and formation processes on the changes of particle density and mixing state.

The vertical distribution of black carbon (BC), as well as its mixing state, is of great concern due to BC's strong regional climatic and environmental effects. In this study, vertical measurements were conducted through a moveable container based on a meteorological tower in the Beijing urban area during June and July. A total of 112 vertical profiles (0–240 m), including the concentrations of BC, O3, NOx and the optical properties of aerosols, were obtained. Based on BC concentration, the vertical profiles could be classified into four categories: uniform, gradual decrease, sharp decrease and sudden increase. The uniform type indicates strong vertical mixing with similar pollutant concentrations along the vertical direction. The gradual and sharp decrease types indicate stable vertical conditions with higher pollutant concentrations on the ground and lower concentrations at higher altitudes. Due to the strong radiation in summer, the vertical profiles exhibited a clear diurnal variation in which ∼ 80 % of profiles were uniform during the daytime and ∼ 40 %–90 % of profiles were of the gradual and sharp decrease types at night. O3 is an exception, and its concentration generally increases with height, even under strong vertical mixing conditions. The size distribution of the BC core varied slightly along the vertical direction, and the coating thickness, denoted by the diameter ratio between the BC-containing particle and BC core (Dp/Dc), of BC increased with height under stable conditions. Although the coating thickness could increase the absorption ability with an average absorption enhancement of 1.25 at 23:00 LT (local time: UTC+8), the vertical difference of Dp/Dc (2 %) was much lower than that of BC concentration (∼ 35 %). The vertical variation in absorption ability was mainly caused by the variation in BC concentration. In addition, O3 and Dp/Dc occasionally increased during 06:00–08:00 but remained stable during 08:00–10:00. Vertical mixing and transportation from upper heights, such as the residual layer, could significantly influence the pollutant properties on the surface during early mornings. This study exhibits a continuous vertical picture of BC and its mixing state in urban areas, which would be helpful for understanding BC's regional environmental effect.

The unprecedented lockdown of human activities during the COVID-19 pandemic has significantly influenced social life in China. However, understanding the impact of this unique event on the emissions of different species is still insufficient, prohibiting the proper assessment of the environmental impacts of COVID-19 restrictions. Here we developed a multi-air-pollutant inversion system to simultaneously estimate the emissions of NOx, SO2, CO, PM2.5 and PM10 in China during COVID-19 restrictions with high temporal (daily) and horizontal (15 km) resolutions. Subsequently, contributions of emission changes versus meteorological variations during the COVID-19 lockdown were separated and quantified. The results demonstrated that the inversion system effectively reproduced the actual emission variations in multi-air pollutants in China during different periods of COVID-19 lockdown, which indicate that the lockdown is largely a nationwide road traffic control measure with NOx emissions decreasing substantially by ∼40 %. However, emissions of other air pollutants were found to only decrease by ∼10 % because power generation and heavy industrial processes were not halted during lockdown, and residential activities may actually have increased due to the stay-at-home orders. Consequently, although obvious reductions of PM2.5 concentrations occurred over the North China Plain (NCP) during the lockdown period, the emission change only accounted for 8.6 % of PM2.5 reductions and even led to substantial increases in O3. The meteorological variation instead dominated the changes in PM2.5 concentrations over the NCP, which contributed 90 % of the PM2.5 reductions over most parts of the NCP region. Meanwhile, our results suggest that the local stagnant meteorological conditions, together with inefficient reductions of PM2.5 emissions, were the main drivers of the unexpected PM2.5 pollution in Beijing during the lockdown period. These results highlighted that traffic control as a separate pollution control measure has limited effects on the coordinated control of O3 and PM2.5 concentrations under current complex air pollution conditions in China. More comprehensive and balanced regulations for multiple precursors from different sectors are required to address O3 and PM2.5 pollution in China.

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.

Biomass burning is one of the key sources of urban aerosols in the North China Plain, especially during winter, when the impact of secondary organic aerosols (SOAs) 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 particulate matter (PM2.5) from urban Tianjin by ultrahigh-resolution Fourier transform ion cyclotron resonanc mass spectrometry (FT-ICR MS). Our results show that most of the CHO and CHON compounds are derived from biomass burning which are poor in oxygen and contain aromatic rings that probably contribute to light-absorbing brown carbon (BrC) 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. However, 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 (OSs) and nitrooxy–organosulfates (nitrooxy–OSs) that are derived from the oxidation of BVOCs. Terpenes may be potential major contributors to organosulfates and nitrooxy–organosulfates. 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 that is associated 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.

Emission inventories are essential for modelling studies and pollution control, but traditional emission inventories are usually updated after a few years based on the statistics of “bottom-up” approach from the energy consumption in provinces, cities, and counties. The latest emission inventories of multi-resolution emission inventory in China (MEIC) was compiled from the statistics for the year 2016 (MEIC_2016). However, the real emissions have varied yearly, due to national pollution control policies and accidental special events, such as the coronavirus disease (COVID-19) pandemic. In this study, a four-dimensional variational assimilation (4DVAR) system based on the “top-down” approach was developed to optimise sulfur dioxide (SO2) emissions by assimilating the data of SO2 concentrations from surface observational stations. The 4DVAR system was then applied to obtain the SO2 emissions during the early period of COVID-19 pandemic (from 17 January to 7 February 2020), and the same period in 2019 over China. The results showed that the average MEIC_2016, 2019, and 2020 emissions were 42.2×106, 40.1×106, and 36.4×106 kg d−1. The emissions in 2020 decreased by 9.2 % in relation to the COVID-19 lockdown compared with those in 2019. For central China, where the lockdown measures were quite strict, the mean 2020 emission decreased by 21.0 % compared with 2019 emissions. Three forecast experiments were conducted using the emissions of MEIC_2016, 2019, and 2020 to demonstrate the effects of optimised emissions. The root mean square error (RMSE) in the experiments using 2019 and 2020 emissions decreased by 28.1 % and 50.7 %, and the correlation coefficient increased by 89.5 % and 205.9 % compared with the experiment using MEIC_2016. For central China, the average RMSE in the experiments with 2019 and 2020 emissions decreased by 48.8 % and 77.0 %, and the average correlation coefficient increased by 44.3 % and 238.7 %, compared with the experiment using MEIC_2016 emissions. The results demonstrated that the 4DVAR system effectively optimised emissions to describe the actual changes in SO2 emissions related to the COVID lockdown, and it can thus be used to improve the accuracy of forecasts.

Secondary organic aerosol (SOA) plays a significant role in atmospheric chemistry. However, little is known about the vertical profiles of SOA in the urban boundary layer (UBL). This knowledge gap constrains the SOA simulation in chemical transport models. Here, the aerosol samples were synchronously collected at 8, 120, and 260 m based on a 325 m meteorological tower in Beijing from 15 August to 10 September 2015. Strict emission controls were implemented during this period for the 2015 China Victory Day parade. Here, we observed that the total concentration of biogenic SOA tracers increased with height. The fraction of SOA from isoprene oxidation increased with height, whereas the fractions of SOA from monoterpenes and sesquiterpenes decreased, and 2,3-dihydroxy-4-oxopentanoic acid (DHOPA), a tracer of anthropogenic SOA from toluene oxidation, also increased with height. The complicated vertical profiles of SOA tracers highlighted the need to characterize SOA within the UBL. The mass concentration of estimated secondary organic carbon (SOC) ranged from 341 to 673 ng C m−3. The increase in the estimated SOC fractions from isoprene and toluene with height was found to be more related to regional transport, whereas the decrease in the estimated SOC from monoterpenes and sesquiterpene with height was more subject to local emissions. Emission controls during the parade reduced SOC by 4 %–35 %, with toluene SOC decreasing more than the other SOC. This study demonstrates that vertical distributions of SOA within the UBL are complex, and the vertical profiles of SOA concentrations and sources should be considered in field and modeling studies in the future.

Ambient air pollution from ozone and fine particulate matter is associated with premature mortality. As emissions from one continent influence air quality over others, changes in emissions can also influence human health on other continents. We estimate global air pollution-related premature mortality from exposure to PM 2.5 and ozone, and the avoided deaths from 20% anthropogenic emission reductions from six source regions, North America (NAM), Europe (EUR), South Asia (SAS), East Asia (EAS), Russia/Belarus/Ukraine (RBU) and the Middle East (MDE), three global emission sectors, Power and Industry (PIN), Ground Transportation (TRN) and Residential (RES) and one global domain (GLO), using an ensemble of global chemical transport model simulations coordinated by the second phase of the Task Force on Hemispheric Transport of Air Pollution (TF-HTAP2), and epidemiologically-derived concentration-response functions. We build on results from previous studies of the TF-HTAP by using improved atmospheric models driven by new estimates of 2010 anthropogenic emissions (excluding methane), with more source and receptor regions, new consideration of source sector impacts, and new epidemiological mortality functions. We estimate 290,000 (95% CI: 30,000, 600,000) premature O 3 -related deaths and 2.8 million (0.5 million, 4.6 million) PM 2.5 -related premature deaths globally for the baseline year 2010. While 20% emission reductions from one region generally lead to more avoided deaths within the source region than outside, reducing emissions from MDE and RBU can avoid more O 3 -related deaths outside of these regions than within, and reducing MDE emissions also avoids more PM 2.5 -related deaths outside of MDE than within. Our findings that most avoided O 3 -related deaths from emission reductions in NAM and EUR occur outside of those regions contrast with those of previous studies, while estimates of PM 2.5 -related deaths from NAM, EUR, SAS and EAS emission reductions agree well. In addition, EUR, MDE and RBU have more avoided O 3 -related deaths from reducing foreign emissions than from domestic reductions. For six regional emission reductions, the total avoided extra-regional mortality is estimated as 6,000 (-3,400, 15,500) deaths/year and 25,100 (8,200, 35,800) deaths/year through changes in O 3 and PM 2.5 , respectively. Interregional transport of air pollutants leads to more deaths through changes in PM 2.5 than in O 3 , even though O 3 is transported more on interregional scales, since PM 2.5 has a stronger influence on mortality. For NAM and EUR, our estimates of avoided mortality from regional and extra-regional emission reductions are comparable to those estimated by regional models for these same experiments. In sectoral emission reductions, TRN emissions account for the greatest fraction (26-53% of global emission reduction) of O 3 -related premature deaths in most regions, in agreement with previous studies, except for EAS (58%) and RBU (38%) where PIN emissions dominate. In contrast, PIN emission reductions have the greatest fraction (38-78% of global emission reduction) of PM 2.5 -related deaths in most regions, except for SAS (45%) where RES emission dominates, which differs with previous studies in which RES emissions dominate global health impacts. The spread of air pollutant concentration changes across models contributes most to the overall uncertainty in estimated avoided deaths, highlighting the uncertainty in results based on a single model. Despite uncertainties, the health benefits of reduced intercontinental air pollution transport suggest that international cooperation may be desirable to mitigate pollution transported over long distances.