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The complex particle morphology of black carbon (BC) induces considerable uncertainties in constraining its optical properties. In particular, the diversity of how the BC core and coating are combined is yet to be resolved due to the lack of direct ambient quantification. In this study, by concurrent measurements of the electrical mobility diameter (Dm) and optical volume‐equivalent diameter (Dve), the dynamic shape factor (χ = Dm/Dve) of ambient BC‐containing particles at different mixing states was quantified for the first time. BC in urban Beijing showed a widely distributed χ of 1.4 ± 0.43. Particles with larger refractory BC (rBC) cores showed higher non‐sphericity and higher χ. A ten‐fold increase in the volume ratio of the coating over rBC (VR) could decrease the fraction of fractal BC by 36%. This study proposed a χ‐VR space to describe the particle shape, which is able to include all ambient quantified BC morphologies in optical model. Plain Language Summary: Black carbon (BC) is an important short‐lived light‐absorbing aerosol component in the atmosphere. Its optical properties are complicated by the complex particle morphology, such as the non‐BC substances associated with it and the combination of BC and non‐BC substances within particle. The previous quantification of particle morphology could not distinguish the information specifically for ambient BC, nor the single BC particle characterization can represent full diversities for all particles. This study used concurrent measurements of volume‐equivalent and mobility diameter of BC‐containing particles (BCc) to characterize the coating content and particle shape online for all BC particles in the ambient environment. As a result, we can include all the measured particle morphology information in optical models. Particles with larger BC cores showed higher non‐sphericity, with a greater discrepancy between the measured absorbing properties and that calculated by the Mie theory. Key Points: The morphology of ambient black carbon‐containing particles was characterized by volume‐equivalent and mobility diameter measurementsBlack carbon with higher coatings showed more spherical shapesA space using coatings and particle shape was developed to incorporate morphology information for all black carbon‐containing particles [ABSTRACT FROM AUTHOR]

The mixing state of refractory black carbon (rBC) aerosols is regarded as a major uncertainty in climate-forcing assessments. This study measured the size distribution and mixing state of rBC using a single-particle soot photometer in the winter of 2022 at an urban site in Beijing. During the campaign, the mean mass concentration of rBC was 0.79 ± 0.63 μg m−3, much lower than that observed in Beijing in the winter of 2013. The number and mass median diameter of the rBC cores were 97 and 200 nm, respectively. The average relative coating thicknesses (RCT) of rBC-containing particles was 1.45 ± 0.27 and average light absorption enhancement (Eabs) was 1.43 ± 0.22. Similar to Eabs, RCT and secondary inorganic aerosols (SIA), especially nitrate, increased with increasing relative humidity. This suggests that higher SIA mass fraction in aerosol with a higher relative humidity in the environment results in a thicker coating and black carbon ageing, thus enhancing light absorption. RCT and Eabs increased rapidly with the increase of PM 1 loading but increased slowly when the PM 1 mass concentration exceeded 60 μg m−3. This indicates that a further increase in the NR-PM 1 species at high PM loading does not increase the thickness of the coatings; therefore, there is no further increase in Eabs. The effects of the chemical composition of the Eabs obtained using the Lindeman, Merenda, and Gold method showed that nitrate plays a prominent role in the enhancement of light absorption, followed by SOA. The rBC mass concentration exhibited clear day-low and night-high patterns which were influenced by the synergetic effects of the boundary layer and emissions. RCT and Eabs presented similar diurnal variations, peaking in the afternoon, which was consistent with the pattern of SIA. This suggests that the SIA produced via photochemical reactions supports the ageing of black carbon-containing particles, leading to light-absorption enhancement. The back-trajectory analysis showed the highest values of rBC mass concentration, RCT, and Eabs appeared in the S cluster suggested that the rBC-containing particles transported from south Beijing were more aged with a thicker coating. While the rBC-containing particles from northern and northwestern Beijing had lower RCT and Eabs values. • Nitrate is the dominant contributor to the coatings on BC and prominent role in light-absorption enhancement. • RCT and Eabs increased rapidly as PM 1 loading increased, but slowly when the PM 1 mass concentration exceeded 60 μg m−3. • The rBC- containing particles transported from south Beijing are more aged with a thicker coating. • ∼15% of the NR-PM 1 mass was bound to BC particles. [ABSTRACT FROM AUTHOR]

The physical properties of black carbon (BC) including the mass loading, size distribution and mixing state were in-situ characterized by aircraft measurements using a single particle soot photometer (SP2) in the lower troposphere over Beijing area. The flights were conducted in both late spring and winter during the daytime with well-developed planetary boundary layer (PBL). The BC mass in the PBL (BC PBL) in late spring showed no apparent vertical gradient nor correlation with the PBL height (PBLH) due to strong convective mixing; in winter the BC PBL was more concentrated near ground and anti-correlated with the PBLH due to dilution effect of the dominant cleaner northerly air masses at higher altitude. The BC mass loading at height h , C(h) within the PBL can be extended from the surface level (C0) in late spring; for levels above the PBL, C(h) can be parameterized by applying an exponential decline function C(h) = C0*exp(h/hs) , with the scale height (hs) of 0.31 ± 0.16 km and 0.66 ± 0.24 km for late spring and winter respectively. This parameterization excluded the profiles for: turbulent conditions when the BC mass was efficiently vented upwards and diluted, expressed as C(h) = C0 up to the top of the PBL; or in periods of strong southerly advection, when the entire column was significantly influenced by regional transport from the polluted south regions. The BC core mass median diameters (MMD) were commonly populated at 205–220 nm in both seasons, with additional mode of MMD ∼195 nm also frequently observed in late spring. The bulk relative coating thickness of BC (coated diameter divided by uncoated core diameter D p /D c) in the PBL mostly populated at 2.0–2.2 but at ∼1.2–1.6 in the lower free troposphere (FT). The mass absorption cross section of BC at 550 nm (MAC550), constrained by the SP2 measurements, was largely influenced by the coating thickness, was relatively consistent in the PBL at ∼8.6 m2 g−1, but reduced to 7–7.5 m2 g−1 in the FT or turbulent condition due to decreased coatings. The BC was found to exhibit smaller particle size in the FT but larger in the PBL, which may imply larger BC have been scavenged by low-level clouds. The BC particles trapped in the PBL or regionally transported from polluted region represent the most absorbing element in the particulate matter population and should be particularly considered in evaluating the radiative forcing impact of aerosols over this region. • Vertical profiles of black carbon physical properties in the lower troposphere were in-situ characterized over Beijing. • Black carbon at different layers was influenced by seasonal emission and meteorological conditions. • These results will improve modelling on black carbon radiative forcing and constrain remote sensing absorption measurement. [ABSTRACT FROM AUTHOR]

Atmospheric loading of black carbon aerosols influences air quality and visibility, and their mixing state and aerosol chemistry were sensitive to both emission scenarios and regional transport. In this study, the aerodynamic size-resolved mixing state of refractory black carbon aerosols (rBC) was investigated using a novel tandem system consisting of an aerodynamic aerosol classifier (AAC), a single particle soot photometer (SP2), and single-particle-aerosol mass spectrometry (SPA-MS) during the XXIV Olympic Winter Games (OWG) at an urban site in Beijing. Particles with aerodynamic diameter (D ae) of 200 nm and 300 nm were selected by AAC to focus on the effect of relative differences in morphology on the coating thickness, coating compositions, and optical properties of rBC particles. We found that rBC-containing particles with D ae of 300 nm were characterized by a rBC core with a count median diameter (CMD) of 108 ± 4 nm that typically have regular morphology (χ : m e a n ∼ 1) , higher relative coating thickness (RCT: mean ∼1.9), and strong light absorption enhancement (E abs : mean ∼1.5). The rBC-containing particles with D ae = 200 nm normally had irregular shapes (χ : m e a n ∼ 1.4) and weak E abs (E abs : mean ∼1.37). Classification based on air mass clustering and air pollution level revealed that the coating thickness of rBC particles only exhibited unimodal patterns under clean air conditions and distinct bimodal distributions under heavy pollution conditions, implying multiple origins of rBC particles, even during OWG periods. The coating thickness and E abs of rBC particles were greater when influenced by the higher RH air from east. Furthermore, the chemical compositions of the rBC coating quantitatively determined by SPA-MS were used to estimate the possible origins of the D ae = 300 nm, featured by a thicker coating thickness and stronger light absorption enhancement. Our results showed that rBC particles were primarily mixed with organics, nitrate, and sulfate during the XXIV OWG period. The organic components have a limited role in increasing rBC coatings under polluted conditions, while the alkali metal ions (K and Na) associated with traffic emissions and the secondary inorganic species favor the formation of thick coatings. Higher RH makes limited contributions to rBC mixed with sulfate and organics only (BCOC*_S) and pure BC. The relatively fresh BC could directly mix with organics and sulfate at low RH levels while evolving to mix with nitrate at high RH conditions. In addition to high concentrations of locally emitted precursors and high RH that tend to form thick coatings of nitrate-related rBC aerosols, secondary transport from the west and southwest also contributes to rBC aerosols mixed with nitrate with relatively thick coatings. • rBC with an aerodynamic diameter (D ae) of 300 nm typically have regular morphology. • rBC of regular shape(D ae = 300 nm)has thicker coatings and stronger absorption enhancement. • During the OWG, rBC particles were primarily mixed with organics, nitrate and sulfate. • rBC particles had multiple sources, even in the OWG periods. • The organic components have a limited role in increasing rBC coatings under polluted conditions. [ABSTRACT FROM AUTHOR]

Black carbon (BC) is the most important aerosol light-absorbing component, and its effect on radiation forcing is determined by its microphysical properties. In this study, two microphysical parameters of refractory BC (rBC), namely, size distribution and mixing state, in urban Beijing from 2013 to 2019 were investigated to understand the effects of source changes over the past years. The mass equivalent diameter of rBC (D c) exhibited bimodal lognormal distributions in all seasons, with the major modes accounting for most (>85%) of the rBC masses. The mass median diameter (MMD) was obviously larger in winter (209 nm) than in summer (167 nm) likely due to the contribution of more rBC with larger D c from solid fuel combustion and enhanced coagulation of rBC in polluted winter. More rBC particles were thickly coated in winter, with the number fraction of thickly coated rBC (f coatBC) ranging within 29%–48% compared with that of 12%–14% in summer. However, no evidential increase in BC light-absorption capability was observed in winter. This finding was likely related to the lower absorption efficiency of larger rBC in winter, which partly offset the coating-induced light enhancement. Two stage of decreases in MMD and f coatBC were observed, accompanied with a persistent decrease in rBC loading, thereby reflecting the discrepant effects of source control measures on rBC loading and physical properties. The control measures in the earlier stage before 2016 was more efficient to reduce the rBC loading but slightly influenced the microphysical properties of rBC. As of 2016, the reduction in rBC concentration slowed down because of its low atmospheric loading. However, rBC showed a more obvious decrease in its core size and became less coated. The decrease in f coatBC may have weakened the BC absorption and accelerated the decrease in light absorption resulting from the reduction in rBC loading. Image 1 Decreases in BC core size and coating fraction were observed in Beijing from 2013 to 2019 in response to clean air actions. [ABSTRACT FROM AUTHOR]

Black carbon (BC) exerts important radiative effects over regions with intensive emissions. This study presents in-situ aircraft measurements of BC vertical profiles including mass loading, size distribution and mixing state, spanning a range of pollution levels in both warm and cold seasons over Beijing. The development of planetary boundary layer (PBL) influenced the properties of pollutants at low levels, and regional transport from the southwest elevated the pollution at higher altitudes. Thicker coatings of BC were associated with higher pollution in the PBL, where interactions between BC and other substances intensively took place. Considering the mixing state of BC, the absorption efficiency could be potentially increased by up to 86% and 60% in the PBL and lower free troposphere, respectively. Including a column-integrated absorption enhancement, the in-situ constrained absorption aerosol optical depth at wavelength 870 nm (AAOD 870) improved the agreement with AERONET by 28%, but the in-situ measurement remained 19% lower. A radiative transfer model finds a BC heating rate of 0.1–0.3 K/d and 0.5–3.1 K/d for less and more polluted environments respectively, and the BC coating effect could positively introduce a +0.1–4.2 Wm-2 radiative forcing. The presence of aerosol layer enhanced the positive vertical gradient of heating rate by redistributing the actinic flux. In particular, this gradient was further enhanced by introducing thickly-coated BC at higher level during the regional transport events, which may promote the temperature inversion and further depress the PBL development on polluted days. • BC mass loading for less polluted Beijing was consistent with urban EU/NA. • BC heating rate in the PBL increased to 0.5-3.1K/d on polluted days and had positive vertical gradient. • BC coatings enhanced the columnar absorption up to 80% with positive radiative forcing +0.1–4.2 Wm-2. [ABSTRACT FROM AUTHOR]

The accurate derivation of the proportion and absorption enhancement of black carbon (BC)-containing aerosols in the atmosphere is critical to assess their effect on air quality and climate. Here, using the field measured size-resolved volatility shrink factor, BC bulk mass concentration and the BC mass fraction in BC-containing particles in winter Beijing, we retrieved and quantified both the number and mass concentration of (1) non-BC, (2) internally mixed BC and (3) externally mixed BC of ambient fine aerosol particles. The reliability of the retrieval method has been evaluated by comparing with the simultaneously measured data. The number fraction of BC-containing particles accounts for 60–78% of ambient fine particles, with internally (both BC core and coating materials) and externally mixed BC of 51–64% and 9–23%, respectively. Only for nucleated particles on clean days, when nucleation is a major source of aerosol particles, did the non-BC component dominate (54%). A large amount of aerosols are BC-containing particles, with mass fraction of 32–52%, suggesting the dominant role of BC in elevating mass concentration of particulate matter (PM) in a polluted urban area. We also show that the BC particles are thickly coated with coating thickness (characterized by D p /D c , ratio of the BC diameter before and after heating at 300 °C) of 1.6–2.2, implying efficient aging of BC particles in polluted urban area. Our results imply a large proportion of BC-containing particles in the atmosphere, which could help towards understanding the role of BC on regional haze formation and climate forcing. Image 1 • Mixing state of BC was retrieved using a new method. • BC-containing particles account for large proportions of ambient fine aerosols. • The BC-containing particles are thickly coated. Main findings of this work: 1. BC-containing particles account for large proportion. 2. The BC-containing particles are thickly coated. [ABSTRACT FROM AUTHOR]