Radiative absorption enhancement of dust mixed with anthropogenic pollution over East Asia

The particle mixing state plays a significant yet poorly quantified role in aerosol radiative forcing, especially for the mixing of dust (mineral absorbing) and anthropogenic pollution (black carbon absorbing) over East Asia. We have investigated the absorption enhancement of mixed-type aerosols over East Asia by using the Aerosol Robotic Network observations and radiative transfer model calculations. The mixed-type aerosols exhibit significantly enhanced absorbing ability than the corresponding unmixed dust and anthropogenic aerosols, as revealed in the spectral behavior of absorbing aerosol optical depth, single scattering albedo, and imaginary refractive index. The aerosol radiative efficiencies for the dust, mixed-type, and anthropogenic aerosols are −101.0, −112.9, and −98.3 Wm⁻²τ⁻¹ at the bottom of the atmosphere (BOA); −42.3, −22.5, and −39.8 Wm⁻²τ⁻¹ at the top of the atmosphere (TOA); and 58.7, 90.3, and 58.5 Wm⁻²τ⁻¹ in the atmosphere (ATM), respectively. The BOA cooling and ATM heating efficiencies of the mixed-type aerosols are significantly higher than those of the unmixed aerosol types over the East Asia region, resulting in atmospheric stabilization. In addition, the mixed-type aerosols correspond to a lower TOA cooling efficiency, indicating that the cooling effect by the corresponding individual aerosol components is partially counteracted. We conclude that the interaction between dust and anthropogenic pollution not only represents a viable aerosol formation pathway but also results in unfavorable dispersion conditions, both exacerbating the regional air pollution in East Asia. Our results highlight the necessity to accurately account for the mixing state of aerosols in atmospheric models over East Asia in order to better understand the formation mechanism for regional air pollution and to assess its impacts on human health, weather, and climate

Radiative absorption enhancement of dust mixed with anthropogenic pollution over East Asia

The particle mixing state plays a significant yet poorly quantified role in aerosol radiative forcing, especially for the mixing of dust (mineral absorbing) and anthropogenic pollution (black carbon absorbing) over East Asia. We have investigated the absorption enhancement of mixed-type aerosols over East Asia by using the Aerosol Robotic Network observations and radiative transfer model calculations. The mixed-type aerosols exhibit significantly enhanced absorbing ability than the corresponding unmixed dust and anthropogenic aerosols, as revealed in the spectral behavior of absorbing aerosol optical depth, single scattering albedo, and imaginary refractive index. The aerosol radiative efficiencies for the dust, mixed-type, and anthropogenic aerosols are −101.0, −112.9, and −98.3 Wm⁻²τ⁻¹ at the bottom of the atmosphere (BOA); −42.3, −22.5, and −39.8 Wm⁻²τ⁻¹ at the top of the atmosphere (TOA); and 58.7, 90.3, and 58.5 Wm⁻²τ⁻¹ in the atmosphere (ATM), respectively. The BOA cooling and ATM heating efficiencies of the mixed-type aerosols are significantly higher than those of the unmixed aerosol types over the East Asia region, resulting in atmospheric stabilization. In addition, the mixed-type aerosols correspond to a lower TOA cooling efficiency, indicating that the cooling effect by the corresponding individual aerosol components is partially counteracted. We conclude that the interaction between dust and anthropogenic pollution not only represents a viable aerosol formation pathway but also results in unfavorable dispersion conditions, both exacerbating the regional air pollution in East Asia. Our results highlight the necessity to accurately account for the mixing state of aerosols in atmospheric models over East Asia in order to better understand the formation mechanism for regional air pollution and to assess its impacts on human health, weather, and climate

Interaction between succinic acid and sulfuric acid–base clusters

Dicarboxylic acids likely participate in the formation of pre-nucleation clusters to facilitate new particle formation in the atmosphere, but the detailed mechanism leading to the formation of multicomponent critical nuclei involving organic acids, sulfuric acid (SA), base species, and water remains unclear. In this study, theoretical calculations are performed to elucidate the interactions between succinic acid (SUA) and clusters consisting of SA-ammonia (AM)∕dimethylamine (DMA) in the presence of hydration of up to six water molecules. Formation of the hydrated SUA•SA• base clusters is energetically favorable, triggering proton transfer from SA to the base molecule to form new covalent bonds or strengthening the preexisting covalent bonds. The presence of SUA promotes hydration of the SA•AM and SA•AM•DMA clusters but dehydration of the SA•DMA clusters. At equilibrium, SUA competes with the second SA molecule for addition to the SA• base clusters at atmospherically relevant concentrations. The clusters containing both the base and organic acid are capable of further binding with acid molecules to promote subsequent growth. Our results indicate that the multicomponent nucleation involving organic acids, sulfuric acid, and base species promotes new particle formation in the atmosphere, particularly under polluted conditions with a high concentration of diverse organic acids

An unexpected catalyst dominates formation and radiative forcing of regional haze

Although regional haze adversely affects human health and possibly counteracts global warming from increasing levels of greenhouse gases, the formation and radiative forcing of regional haze on climate remain uncertain. By combining field measurements, laboratory experiments, and model simulations, we show a remarkable role of black carbon (BC) particles in driving the formation and trend of regional haze. Our analysis of long-term measurements in China indicates declined frequency of heavy haze events along with significantly reduced SO₂, but negligibly alleviated haze severity. Also, no improving trend exists for moderate haze events. Our complementary laboratory experiments demonstrate that SO₂ oxidation is efficiently catalyzed on BC particles in the presence of NO₂ and NH₃, even at low SO₂ and intermediate relative humidity levels. Inclusion of the BC reaction accounts for about 90–100% and 30–50% of the sulfate production during moderate and heavy haze events, respectively. Calculations using a radiative transfer model and accounting for the sulfate formation on BC yield an invariant radiative forcing of nearly zero W m⁻² on the top of the atmosphere throughout haze development, indicating small net climatic cooling/warming but large surface cooling, atmospheric heating, and air stagnation. This BC catalytic chemistry facilitates haze development and explains the observed trends of regional haze in China. Our results imply that reduction of SO₂ alone is insufficient in mitigating haze occurrence and highlight the necessity of accurate representation of the BC chemical and radiative properties in predicting the formation and assessing the impacts of regional haze

Aerosol vertical distribution and optical properties over China from long-term satellite and ground-based remote sensing

The seasonal and spatial variations of vertical distribution and optical properties of aerosols over China are studied using long-term satellite observations from the Cloud–Aerosol Lidar with Orthogonal Polarization (CALIOP) and ground-based lidar observations and Aerosol Robotic Network (AERONET) data. The CALIOP products are validated using the ground-based lidar measurements at the Semi-Arid Climate and Environment Observatory of Lanzhou University (SACOL). The Taklamakan Desert and Tibetan Plateau regions exhibit the highest depolarization and color ratios because of the natural dust origin, whereas the North China Plain, Sichuan Basin and Yangtze River Delta show the lowest depolarization and color ratios because of aerosols from secondary formation of the anthropogenic origin. Certain regions, such as the North China Plain in spring and the Loess Plateau in winter, show intermediate depolarization and color ratios because of mixed dust and anthropogenic aerosols. In the Pearl River Delta region, the depolarization and color ratios are similar to but higher than those of the other polluted regions because of combined anthropogenic and marine aerosols. Long-range transport of dust in the middle and upper troposphere in spring is well captured by the CALIOP observations. The seasonal variations in the aerosol vertical distributions reveal efficient transport of aerosols from the atmospheric boundary layer to the free troposphere because of summertime convective mixing. The aerosol extinction lapse rates in autumn and winter are more positive than those in spring and summer, indicating trapped aerosols within the boundary layer because of stabler meteorological conditions. More than 80 % of the column aerosols are distributed within 1.5 km above the ground in winter, when the aerosol extinction lapse rate exhibits a maximum seasonal average in all study regions except for the Tibetan Plateau. The aerosol extinction lapse rates in the polluted regions are higher than those of the less polluted regions, indicating a stabilized atmosphere due to absorptive aerosols in the polluted regions. Our results reveal that the satellite and ground-based remote-sensing measurements provide the key information on the long-term seasonal and spatial variations in the aerosol vertical distribution and optical properties, regional aerosol types, long-range transport and atmospheric stability, which can be utilized to more precisely assess the direct and indirect aerosol effects on weather and climate

Remarkable nucleation and growth of ultrafine particles from vehicular exhaust

High levels of ultrafine particles (UFPs; diameter of less than 50 nm) are frequently produced from new particle formation under urban conditions, with profound implications on human health, weather, and climate. However, the fundamental mechanisms of new particle formation remain elusive, and few experimental studies have realistically replicated the relevant atmospheric conditions. Previous experimental studies simulated oxidation of one compound or a mixture of a few compounds, and extrapolation of the laboratory results to chemically complex air was uncertain. Here, we show striking formation of UFPs in urban air from combining ambient and chamber measurements. By capturing the ambient conditions (i.e., temperature, relative humidity, sunlight, and the types and abundances of chemical species), we elucidate the roles of existing particles, photochemistry, and synergy of multipollutants in new particle formation. Aerosol nucleation in urban air is limited by existing particles but negligibly by nitrogen oxides. Photooxidation of vehicular exhaust yields abundant precursors, and organics, rather than sulfuric acid or base species, dominate formation of UFPs under urban conditions. Recognition of this source of UFPs is essential to assessing their impacts and developing mitigation policies. Our results imply that reduction of primary particles or removal of existing particles without simultaneously limiting organics from automobile emissions is ineffective and can even exacerbate this problem

Remarkable nucleation and growth of ultrafine particles from vehicular exhaust

High levels of ultrafine particles (UFPs; diameter of less than 50 nm) are frequently produced from new particle formation under urban conditions, with profound implications on human health, weather, and climate. However, the fundamental mechanisms of new particle formation remain elusive, and few experimental studies have realistically replicated the relevant atmospheric conditions. Previous experimental studies simulated oxidation of one compound or a mixture of a few compounds, and extrapolation of the laboratory results to chemically complex air was uncertain. Here, we show striking formation of UFPs in urban air from combining ambient and chamber measurements. By capturing the ambient conditions (i.e., temperature, relative humidity, sunlight, and the types and abundances of chemical species), we elucidate the roles of existing particles, photochemistry, and synergy of multipollutants in new particle formation. Aerosol nucleation in urban air is limited by existing particles but negligibly by nitrogen oxides. Photooxidation of vehicular exhaust yields abundant precursors, and organics, rather than sulfuric acid or base species, dominate formation of UFPs under urban conditions. Recognition of this source of UFPs is essential to assessing their impacts and developing mitigation policies. Our results imply that reduction of primary particles or removal of existing particles without simultaneously limiting organics from automobile emissions is ineffective and can even exacerbate this problem

Formation and optical properties of brown carbon from small α-dicarbonyls and amines

Brown Carbon (BrC) aerosols scatter and absorb solar radiation, directly affecting the Earth’s radiative budget. However, considerable uncertainty exists concerning the chemical mechanism leading to BrC formation and their optical properties. In this work, BrC particles were prepared from mixtures of small α-dicarbonyls (glyoxal and methylglyoxal) and amines (methylamine, dimethylamine, and trimethylamine). The absorption and scattering of BrC particles were measured using a photoacoustic extinctometer (405 and 532 nm), and the chemical composition of the α-dicarbonyl-amine mixtures was analyzed using orbitrap-mass spectrometry and thermal desorption-ion drift-chemical ionization mass spectrometry. The single scattering albedo for methylglyoxal-amine mixtures is smaller than that of glyoxal-amine mixtures and increases with the methyl substitution of amines. The mass absorption cross-section for methylglyoxal-amine mixtures is two times higher at 405 nm wavelength than that at 532 nm wavelength. The derived refractive indexes at the 405 nm wavelength are 1.40–1.64 for the real part and 0.002–0.195 for the imaginary part. Composition analysis in the α-dicarbonyl-amine mixtures reveals N-heterocycles as the dominant products, which are formed via multiple steps involving nucleophilic attack, steric hindrance, and dipole–dipole interaction between α-dicarbonyls and amines. BrC aerosols, if formed from the particle-phase reaction of methylglyoxal with methylamine, likely contribute to atmospheric warming