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Vehicle emission is a major source of atmospheric secondary organic aerosols (SOA). Driving condition is a critical influencing factor for vehicular SOA production, but few studies have revealed SOA production dependence on the rapidly-changing real-world driving conditions. Here, a fast-response oxidation flow reactor system is developed and deployed to quantify the SOA formation potential under transient driving conditions. Results show that the SOA potential varies by orders of magnitude, e.g., 20-1500 mg kg-fuel-1 and 12–155 mg kg-fuel-1 for China V and China VI vehicles, respectively. High speed, acceleration, and deceleration are found to considerably promote SOA production due to higher organic gaseous emissions caused by unburned fuel emission or incomplete combustion. In addition, China VI vehicles significantly reduce SOA potential, yield, and acceleration and deceleration peaks. Our study provides experimental insight into vehicular SOA formation under transient driving conditions, which would benefit high-time-resolved SOA simulations in the urban atmosphere.

During the pre-monsoon season, biomass burning (BB) activities are intensive in southern Asia. Facilitated by westerly circulation, those BB plumes can be transported to the Tibetan Plateau (TP). Black carbon (BC), the main aerosol species in BB emissions, is an important climate warming agent, and its absorbing property strongly depends on its size distribution and mixing state. To elucidate the influence of those transported BB plumes on the TP, a field campaign was conducted on the southeast edge of the TP during the pre-monsoon season. It was found that the transported BB plumes substantially increased the number concentration of the atmospheric BC particles by a factor of 13 and greatly elevated the number fraction of thickly coated BC from 52 % up to 91 %. Those transported BC particles had slightly larger core size and much thicker coatings than the background BC particles. However, the coating mass was not evenly distributed on BC particles with different sizes. The smaller BC cores were found to have larger shell / core ratios than the larger cores. Besides, the transported BB plumes strongly affected the vertical variation in the BC's abundance and mixing state, resulting in a higher concentration, larger number fraction, and higher aging degree of BC particles in the upper atmosphere. Resulting from both increase in BC loading and aging degree, the transported BB plumes eventually enhanced the total light absorption by a factor of 15, of which 21 % was contributed by the BC aging, and 79 % was contributed from the increase in BC mass. Particularly, the light absorption enhancement induced by the aging process during long-range transport has far exceeded the background aerosol light absorption, which implicates a significant influence of BC aging on climate warming over the TP region.

Large uncertainties remain when estimating the radiative forcing by black carbon (BC) because the corresponding microphysical properties have not been well addressed. In this study, the BC size distributions were studied based on three different field campaigns at an urban site, a suburban site, and a background site in China using a single particle soot photometer (SP2) in tandem with a differential mobility diameter. Measurement results indicate that the BC particles were composed of either thinly or thickly coated aerosols. The mean number fractions of the thinly coated BC aerosols were 51 %, 67 %, and 21 % for the urban, suburban, and background sites, respectively. The corresponding thickly coated (thinly coated) core mass median diameters were 187 (154), 182 (146), and 238 (163) nm, respectively. The mean diameter of the thickly coated BC-containing aerosols was larger than that of the thinly coated BC-containing aerosols, while the mean BC core diameter of the thickly coated BC-containing aerosols was smaller than that of the thinly coated BC-containing aerosols. About 10 % of the BC-containing aerosols with the BC core are attached to the other non-BC components, which were mainly generated by coagulation between the BC and non-BC components. The measurement results in our study can be further used in modeling studies to help with constraining the uncertainties of the BC radiative effects.

Significance High concentrations of ultrafine particles (UFPs), approaching 1 million/cm3, are frequently produced from new particle formation under urban environments, but the fundamental mechanisms regulating nucleation and growth for UFPs are poorly understood. From simultaneous ambient and environmental chamber measurements, we demonstrate remarkable formation of UFPs from urban traffic emissions. By replicating ambient conditions using an environmental chamber method, we elucidate the roles of existing particles, photochemistry, and synergy of multipollutant photooxidation in nucleation and growth of UFPs. Our results reveal that synergetic oxidation of vehicular exhaust leads to efficient formation of UFPs under urban conditions. Recognition of this large urban source for UFPs is essential to accurately assessing their impacts and to effectively developing mitigation policies., 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.

Black carbon (BC) particles exert a significant influence on the earth's climate system. However, large uncertainties remain when estimating the radiative forcing by BC because the corresponding microphysical properties have not been well addressed. Knowleadge of the BC mixing states of different aging degree can help better characterise the corresponding environmental and climate effects. In this study, the BC size distributions were studied based on three different field campaigns at an urban site, a suburban site, and a background site in China using a single particle soot photometer (SP2) in tandem with a differential mobility diameter. Measurements from the SP2 indicate that the BC particles were composed of either fresh or aged aerosols. The mean number fractions of the fresh BC aerosols were 51 %, 67 %, and 21 % for the urban, suburban, and background sites, respectively. The corresponding mobility diameters of these aged (fresh) BC-containing aerosols were 294 nm (193 nm), 244 nm (161 (nm), and 257 nm (162 nm). The measured aged (fresh) BC core number median diameters were 115 nm (114 nm), 107 nm (95 nm), and 127 nm (111 nm) for urban, suburban, and background sites, respectively. The corresponding aged (fresh) core mass median diameters were 187 nm (154 nm), 182 nm (146 nm), and 238 nm (163 nm) respectively. The mean diameter of the aged BC-containing aerosols was larger than that of the fresh BC-containing aerosols, while the mean BC core diameter of the aged BC-containing aerosols was smaller than that of the fresh BC-containing aerosols. About 10 % of the BC-containing aerosols with the BC core were attached to the other non-BC components, which were mainly generated by coagulation between the BC and non-BC components. The measurement results in our study can help better understand the BC size distributions and mixing status in the different atmospheres in China and can be further used in modeling studies to help constrain the uncertainties of the BC radiative effects.

Light-absorbing aerosols (LAA), including black carbon (BC) and brown carbon (BrC), profoundly impact regional and global climate. Vehicle emission is an important source of LAA in urban areas, but real-world emission features of LAA from the urban vehicle fleet are not fully understood. This study evaluates traffic-related BC and BrC emission factors (EFs) and their vehicular emission inventories via road tunnel measurements in Tianjin, China, in 2017 and 2021. The distance-based and fuel-based EFs of BC for the mixed fleet were 1.05 ± 1.28 mg km

The refractive index of ambient aerosols is widely used in the climate model and remote sensing. Traditionally, the real part of the refractive index (RRI) of the ambient aerosol is calculated from the measured mass fraction of the main inorganic components with known refractive index, without full resolving the effects of variation in the RRI of organic components, which always contribute more than 50 % of the total aerosol mass. For the first time, the ambient aerosol RRI and the aerosol chemical components were measured concurrently at a suburban site Changping, in Beijing, China. Measurements results show that the ambient aerosol ranges between 1.57 and 1.71 with a mean value of 1.66. The mean mass fractions of organic aerosol (OA), nitrate, sulfate, ammonium, and chloride to total non-refractory aerosol loading are 43.1 %, 21.9 %, 21.6 %, 13.1 %, and 0.3 % respectively. Source appointment analysis of the organic aerosol show that the fossil fuel-related OA, cooking OA, biomass burning OA, less oxidized oxygenated OA and more oxidized OOA contributes 18.0 %, 11.2 %, 4.1 %, 39.9 %, 26.7 % to the total aerosol. A new parameterization scheme of the ambient aerosol RRI, which considers the source appointed OA, is proposed based on the concurrent measurements of RRI and chemical composition. The measured and parameterized RRI shows good consistency with a correlation coefficient of 0.79 and slope of 0.98. Our measurement results reveal that a significant deviation of the calculated RRI exists without considering the variation of the RRI of the aerosol organic component. The parametrization scheme is adopted and applicable in aerosol model for bettering estimating the corresponding optical and radiative effects.

Nitro-aromatic compounds (NACs), as important contributors to the light absorption by brown carbon, have been widely observed in various ambient atmospheres; however, their formation in the urban atmosphere was little studied. In this work, we report an intensive field study of NACs in summer 2016 at an urban Beijing site, characterized by both high- NOx and anthropogenic VOC dominated conditions. We investigated the factors that influence NAC formation (e.g., NO2 , VOC precursors, RH and photolysis) through quantification of eight NACs, along with major components in fine particulate matter, selected volatile organic compounds, and gases. The average total concentration of the quantified NACs was 6.63 ng m −3 , higher than those reported in other summertime studies (0.14–6.44 ng m −3 ). 4-Nitrophenol (4NP, 32.4 %) and 4-nitrocatechol (4NC, 28.5 %) were the top two most abundant NACs, followed by methyl-nitrocatechol (MNC), methyl-nitrophenol (MNP), and dimethyl-nitrophenol (DMNP). The oxidation of toluene and benzene in the presence of NOx was found to be a more dominant source of NACs than primary biomass burning emissions. The NO2 concentration level was found to be an important factor influencing the secondary formation of NACs. A transition from low- to high- NOx regimes coincided with a shift from organic- to inorganic-dominated oxidation products. The transition thresholds were NO2 ∼ 20 ppb for daytime and NO2∼25 ppb for nighttime conditions. Under low- NOx conditions, NACs increased with NO2 , while the NO 3 - concentrations and ( NO 3 - ) / NACs ratios were lower, implying organic-dominated products. Under high- NOx conditions, NAC concentrations did not further increase with NO2 , while the NO 3 - concentrations and ( NO 3 - ) / NACs ratios showed increasing trends, signaling a shift from organic- to inorganic-dominated products. Nighttime enhancements were observed for 3M4NC and 4M5NC, while daytime enhancements were noted for 4NP, 2M4NP, and DMNP, indicating different formation pathways for these two groups of NACs. Our analysis suggested that the aqueous-phase oxidation was likely the major formation pathway of 4M5NC and 3M5NC, while photo-oxidation of toluene and benzene in the presence of NO2 could be more important for the formation of nitrophenol and its derivatives. Using the (3M4NC + 4M5NC) ∕ 4NP ratios as an indicator of the relative contribution of aqueous-phase and gas-phase oxidation pathways to NAC formation, we observed that the relative contribution of aqueous-phase pathways increased at elevated ambient RH and remained constant at RH > 30 %. We also found that the concentrations of VOC precursors (e.g., toluene and benzene) and aerosol surface area acted as important factors in promoting NAC formation, and photolysis as an important loss pathway for nitrophenols.

To investigate aerosol optical properties relevant to pollutant level controls in place in Beijing, particulate matters with diameter σ a p ) and scattering ( σ s p ) coefficients were continuously measured from January 2014 to March 2017 at an urban site Peking University Atmosphere Environment MonitoRing Station (PKUERS). Our results showed that PM2.5, σ a p , and σ s p all decreased, especially from 2014 to 2015. Note that, a significant decrease of σ a p in autumn and σ s p in winter was responsible for the decrease of the year by year average. PM2.5, σ a p and σ s p exhibited a pronounced bi-peak diurnal variation, which was attributed to the traffic emissions. The wind dependence analysis revealed that σ a p was mainly influenced by local emissions but σ s p was influenced by both local emissions and regional transport. The potential spatial source origins of σ s p in Beijing were investigated using the potential source contribution function (PSCF). The results indicated that the potential source regions that influence σ s p of Beijing were mainly from south and west of Beijing but slightly varied with different years and seasons.

Severe haze events with exceedingly high-levels of fine aerosols occur frequently over the past decades in the North China Plain (NCP), exerting profound impacts on human health, weather, and climate. The development of effective mitigation policies requires a comprehensive understanding of the haze formation mechanisms, including identification and quantification of the sources, formation, and transformation of the aerosol species. Haze evolution in this region exhibits distinct physical and chemical characteristics from clean to polluted periods, as evident from increasing stagnation and relative humidity, but decreasing solar radiation as well as explosive secondary aerosol formation. The latter is attributed to highly elevated concentrations of aerosol precursor gases and is reflected by rapid increases in the particle number and mass concentrations, both corresponding to nonequilibrium chemical processes. Considerable new knowledge has been acquired to understand the processes regulating haze formation, particularly in light of the progress in elucidating the aerosol formation mechanisms. This review synthesizes recent advances in understanding secondary aerosol formation, by highlighting several critical chemical/physical processes, that is, new particle formation and aerosol growth driven by photochemistry and aqueous chemistry as well as the interaction between aerosols and atmospheric stability. Current challenges and future research priorities are also discussed.

During the pre-monsoon season, biomass burning (BB) activities are intensive in southern Asia. Facilitated by westerly circulation, those BB plumes can be transported to the Tibetan Plateau (TP). Black carbon (BC), the main aerosol species in BB emissions, is an important climate warming agent, and its absorbing property strongly depends on its size distribution and mixing state. To elucidate the influence of those transported BB plumes on the TP, a field campaign was conducted on the southeast edge of the TP during the pre-monsoon season. It was found that the transported BB plumes substantially increased the number concentration of the atmospheric BC particles by 13 times, and greatly elevated the number fraction of thickly-coated BC from 52 % up to 91 %. Those transported BC particles had slightly larger core size and much thicker coatings than the background BC particles. However, the coating mass was not evenly distributed on BC particles with different sizes. The smaller BC cores were found to have larger shell/core ratios than the larger cores. Besides, the transported BB plumes strongly affected the vertical variation of the BC's abundance and mixing state, resulting in a higher concentration, larger number fraction and higher aging degree of BC particles in the upper atmosphere. Resulted from both increase of BC loading and aging degree, the transported BB plumes eventually enhanced the total light absorption by 15 times, in which 21 % was contributed by the BC aging and 79 % was contributed from the increase of BC mass. Particularly, the light absorption enhancement induced by the aging process during long-range transport has far exceeded the background aerosol light absorption, which implicates a significant influence of BC aging on climate warming over the TP region.

Light-duty gasoline vehicles have drawn public attention in China due to their significant primary emissions of particulate matter and volatile organic compounds (VOCs). However, little information on secondary aerosol formation from exhaust for Chinese vehicles and fuel conditions is available. In this study, chamber experiments were conducted to quantify the potential of secondary aerosol formation from the exhaust of a port fuel injection gasoline engine. The engine and fuel used are common in the Chinese market, and the fuel satisfies the China V gasoline fuel standard. Substantial secondary aerosol formation was observed during a 4–5 hr simulation, which was estimated to represent more than 10 days of equivalent atmospheric photo-oxidation in Beijing. As a consequence, the extreme case secondary organic aerosol (SOA) production was 426 ± 85 mg/kg-fuel, with high levels of precursors and OH exposure. The low hygroscopicity of the aerosols formed inside the chamber suggests that SOA was the dominant chemical composition. Fourteen percent of SOA measured in the chamber experiments could be explained through the oxidation of speciated single-ring aromatics. Unspeciated precursors, such as intermediate-volatility organic compounds and semi-volatile organic compounds, might be significant for SOA formation from gasoline VOCs. We concluded that reductions of emissions of aerosol precursor gases from vehicles are essential to mediate pollution in China.

The substitution of long-distance road transportation by railways, so-called the “road-to-rail” policy, is one of the major national regulatory policies for atmospheric pollution mitigation in China. However, owing to the lack of real-world diesel locomotive emission measurements, the environmental benefits of the “road-to-rail” policy have not been well evaluated. In this study, emissions from 245 in-use line-haul diesel locomotives (including three types of DF4, HX3, and HX5) were measured under real-world conditions via a railway tunnel observation conducted in Beijing on September 7–13, 2017. The fuel-specific and distance-specific emission factors (EFs) of NOx, CO, SO2, and BC were determined by using the carbon balance and mass conservation methods, respectively. The measured EFs of NOx and CO for the HX series locomotives were 41% and 30% higher than the Tire 2 emission standard limits respectively. Based on the two sets of EFs and corresponding activity levels, total locomotive emissions of NOx and CO in China in 2018 were approximately 17.36–19.23 × 104 t and 4.76–5.69 × 104 t respectively. Scenario analysis based on the fuel life cycle shows that all “road-to-rail” scenarios reduce the total energy consumption and pollutant emissions in the short term. For the scenario maintaining the current proportion (20%) of diesel locomotives, the “road-to-rail” policy may reduce NOx and BC emissions by 7.03–70.33 × 104 t/year and 0.10–1.02 × 104 t/year respectively. Considering the upgradation of emission standards with heavy-duty diesel vehicles, the air quality improvement benefit of the “road-to-rail” policy may only be sustained for 2–3 years and 8 years respectively, under the full diesel locomotive scenario and the current diesel locomotive scenario. We highlight the necessity of a more careful and accurate estimation of “road-to-rail” policy environmental benefits to obtain better air quality and the greatest health benefits.

The real part of the refractive index (RRI) of ambient aerosol, which is widely used in remote sensing and atmospheric models, is one of the key factors determining its particles' optical properties. The characteristics of ambient aerosol RRI in China have not yet been well studied owing to a lack of observations. For the first time, the properties of aerosol RRI were studied based on field measurements in China at four sites with different atmospheres. The results revealed that the measured ambient aerosol RRI varied significantly between 1.36 and 1.78, increasing with the mass ratio of organic components. The scattering coefficient and direct radiative effects of the aerosols were estimated to increase by factors of 2 and 3, respectively, when RRI increased from 1.36 to 1.78. Our results indicate that variation in ambient aerosol RRI should be considered in aerosol and climate models to achieve an accurate estimation of aerosol's radiative impacts.

Highly time-resolved in situ measurements of airborne particles were conducted at Mt. Yulong (3410 m above sea level) on the southeastern edge of the Tibetan Plateau in China from 22 March to 14 April 2015. The detailed chemical composition was measured by a high-resolution time-of-flight aerosol mass spectrometer together with other online instruments. The average mass concentration of the submicron particles (PM1) was 5.7 ± 5.4 µg m−3 during the field campaign, ranging from 0.1 up to 33.3 µg m−3. Organic aerosol (OA) was the dominant component in PM1, with a fraction of 68 %. Three OA factors, i.e., biomass burning organic aerosol (BBOA), biomass-burning-influenced oxygenated organic aerosol (OOA-BB) and oxygenated organic aerosol (OOA), were resolved using positive matrix factorization analysis. The two oxygenated OA factors accounted for 87 % of the total OA mass. Three biomass burning events were identified by examining the enhancement of black carbon concentrations and the f60 (the ratio of the signal at m∕z 60 from the mass spectrum to the total signal of OA). Back trajectories of air masses and satellite fire map data were integrated to identify the biomass burning locations and pollutant transport. The western air masses from South Asia with active biomass burning activities transported large amounts of air pollutants, resulting in elevated organic concentrations up to 4-fold higher than those of the background conditions. This study at Mt. Yulong characterizes the tropospheric background aerosols of the Tibetan Plateau during pre-monsoon season and provides clear evidence that the southeastern edge of the Tibetan Plateau was affected by the transport of anthropogenic aerosols from South Asia.

To elucidate the influence of long-range transported biomass burning organic aerosols (BBOA) on the Tibetan Plateau, the molecular compositions and light absorption of HUmic-Like Substances (HULIS), major fractions of brown carbon, were characterized during the premonsoon season. Under the significant influence of biomass burning, HULIS concentrations increased to as high as 26 times of the background levels, accounting for 54% of water-soluble organic carbon (WSOC) and 50% of organic carbon (OC). The light absorption of HULIS also enhanced up to 42 times of the background levels, contributing 61% of the WSOC absorption and 50% of OC absorption. Meanwhile, elevated nitrogen-containing compounds (NOCs) among HULIS were observed. The NOCs from fresh and aged BBOA were unambiguously identified on the molecular level, through comparing with the molecular compositions of NOCs from lab-controlled and field burning experiments. N-Heterocyclic bases represent major fractions in the reduced nitrogen compounds from fresh BBOA, and nitroaromatic compounds are important groups among the oxidized nitrogen compounds from aged BBOA. The nitrogen-containing compounds, including nitroaromatics and N-heterocyclic compounds, were also important chromophores, which contributed to the enhanced light absorption of extracted HULIS during biomass burning-influenced periods.

As has been the case in North America and Western Europe, the SO2 emissions substantially reduced in North China Plain (NCP) in recent years. A dichotomy of reductions in SO2 and NOx concentrations result in the frequent occurrences of nitrate (pNO3−)-dominated particulate matter pollution over NCP. In this study, we observed a polluted episode with the nitrate mass fraction in non-refractory PM1 (NR-PM1) up to 44 % during wintertime in Beijing. Based on this typical pNO3−-dominated haze event, the linkage between aerosol water uptake and pNO3− formation, further impacting on visibility degradation, have been investigated based on field observations and theoretical calculations. During haze development, as ambient relative humidity (RH) increased from ~ 10 % up to 70 %, the aerosol particle liquid water increased from ~ 1 μg/m3 at the beginning to ~ 75 μg/m3 at the fully-developed haze period. Without considering the water uptake, the particle surface area and the volume concentrations increased by a factor of 4.1 and 4.8, respectively, during the development of haze event. Taking water uptake into account, the wet particle surface area and volume concentrations enhanced by a factor of 4.7 and 5.8, respectively. As a consequence, the hygroscopic growth of particles facilitated the condensational loss of dinitrogen pentoxide (N2O5) and nitric acid (HNO3) to particles contributing pNO3−. From the beginning to the fully-developed haze, the condensational loss of N2O5 increased by a factor of 20 when only considering aerosol surface area and volume of dry particles, while increasing by a factor of 25 considering extra surface area and volume due to water uptake. Similarly, the condensational loss of HNO3 increased by a factor of 2.7~2.9 and 3.1~3.5 for dry and wet aerosol surface area and volume from the beginning to the fully-developed haze period. Above results demonstrated that the pNO3− formation is further enhanced by aerosol water uptake with elevated ambient RH during haze development, in turn, facilitating the aerosol taking up water due to the hygroscopicity of nitrate salt. Such mutual promotion effect between aerosol particle liquid water and nitrate formation can rapidly degrade air quality and halve visibility within one day. Reduction of nitrogen-containing gaseous precursors, e.g., by control of traffic emissions, is essential in mitigating severe haze events in NCP.

Nitro-aromatic compounds (NACs), as important contributors to ultraviolet light absorption by brown carbon, have been widely observed in various ambient atmospheres, however, few field studies has been focused on their formation in urban atmospheres. In this work, NACs in Beijing were comprehensively quantified and characterized in summer, along with major components in fine particulate matter and selected volatile organic compounds. Field observations in this high NOx-anthropogenic VOCs dominated urban atmosphere were analyzed to investigate the NAC formation and influence factors. The total concentration of quantified NACs was 6.63 ng/m3, higher than other summertime studies (0.14–6.44 ng/m3). 4-Nitrophenol (4NP, 32.4 %) and 4-nitrocatechol (4NC, 28.5 %) were the most abundant ones among all the quantified NAC species, followed by methyl-nitrocatechol (MNC), methyl-nitrophenol (MNP) and dimethyl-nitrophenol (DMNP). The oxidation of toluene and benzene in the presence of NOx were found to be more dominant sources of NACs than biomass burning emissions. The NO2 level was an important factor influencing the secondary formation of NACs. A transition from low- to high-NOx regimes coincided with a shift from organic- to inorganic-dominated oxidation products. The transition thresholds were NO2∼20 ppb for daytime and NO2∼25 ppb for nighttime conditions. Under low-NOx conditions, NACs increased with NO2, while the NO3− concentrations and (NO3−)/NACs ratios were lower, implying organic-dominated products. Above the NOx regime transition values, NO2 was excess for the oxidation of ambient VOCs. Under this condition, NAC concentrations did not further increase obviously with NO2, while the NO3− concentrations and (NO3−)/NACs ratios showed significant increasing trends, when shifting from organic- to inorganic-dominated products. Obvious nighttime enhancements of 3M4NC and 4M5NC, daytime enhancements of 4NP, 2M4NP and DMNP indicated their different formation pathways. The aqueous-phase oxidation was the major formation pathways of 4M5NC and 3M5NC, and photo-oxidation of toluene and benzene in the presence of NO2 could be more important for the formation of nitrophenol and its derivatives. Thus, the (3M4NC + 4M5NC)/4NP ratios was employed to indicate the relative contribution of aqueous-phase and gas-phase oxidation to NAC formation. The relative contribution of aqueous-phase pathways was observed to increase at elevated ambient RH and remain constant at RH > 30 %. In addition, the concentrations of VOC precursors (e.g. toluene and benzene) and aerosol surface area were also important factors promoting NAC formation, and photolysis was an important loss pathway of NACs.

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.

Sulfate aerosols exert profound impacts on human and ecosystem health, weather, and climate, but their formation mechanism remains uncertain. Atmospheric models consistently underpredict sulfate levels under diverse environmental conditions. From atmospheric measurements in two Chinese megacities and complementary laboratory experiments, we show that the aqueous oxidation of SO_2 by NO_2 is key to efficient sulfate formation but is only feasible under two atmospheric conditions: on fine aerosols with high relative humidity and NH_3 neutralization or under cloud conditions. Under polluted environments, this SO_2 oxidation process leads to large sulfate production rates and promotes formation of nitrate and organic matter on aqueous particles, exacerbating severe haze development. Effective haze mitigation is achievable by intervening in the sulfate formation process with enforced NH_3 and NO_2 control measures. In addition to explaining the polluted episodes currently occurring in China and during the 1952 London Fog, this sulfate production mechanism is widespread, and our results suggest a way to tackle this growing problem in China and much of the developing world.

Black carbon (BC) exerts profound impacts on air quality and climate because of its high absorption cross-section over a broad range of electromagnetic spectra, but the current results on absorption enhancement of BC particles during atmospheric aging remain conflicting. Here, we quantified the aging and variation in the optical properties of BC particles under ambient conditions in Beijing, China, and Houston, United States, using a novel environmental chamber approach. BC aging exhibits two distinct stages, i.e., initial transformation from a fractal to spherical morphology with little absorption variation and subsequent growth of fully compact particles with a large absorption enhancement. The timescales to achieve complete morphology modification and an absorption amplification factor of 2.4 for BC particles are estimated to be 2.3 h and 4.6 h, respectively, in Beijing, compared with 9 h and 18 h, respectively, in Houston. Our findings indicate that BC under polluted urban environments could play an essential role in pollution development and contribute importantly to large positive radiative forcing. The variation in direct radiative forcing is dependent on the rate and timescale of BC aging, with a clear distinction between urban cities in developed and developing countries, i.e., a higher climatic impact in more polluted environments. We suggest that mediation in BC emissions achieves a cobenefit in simultaneously controlling air pollution and protecting climate, especially for developing countries.

Biomass burning (BB) activities have a great impact on particle number size distribution (PNSD) in upper troposphere of Tibet-Plateau, which could affect regional and global climate. The intensive campaign for the measurement of PNSD, gaseous pollutants and meteorological parameters was conducted at Mt. Yulong, a high-altitude site (3410 m a.s.l.) in the southeast of Tibet Plateau during the pre-monsoon season (22 March to 15 April), when the intensive BB activities in South Asia were observed by fire maps. Long-range transport of BB pollutants could increase the accumulation mode particles in background atmosphere of Mt. Yulong. As a consequence, cloud condensation nuclei (CCN) concentration was found to be 2–8 times higher during BB periods than that during clean period. Apart from BB, variation of planet boundary layer (PBL) and new particle formation were other factors that influenced PNSD. However, only 3 NPF events (with a frequency of 14 %) were observed at Mt. Yulong. Occurrence of NPF events during clean episode corresponded with elevated PBL or transported BB pollutants. Due to lack of condensable vapors including sulfuric acid and organic compounds, the newly formed particles were not able to grow to CCN size. Our study emphasized the influences of BB on aerosol and CCN concentration in atmosphere of Tibet Plateau. These results can improve our understanding of the variation of particle concentration in upper troposphere, and provide information for regional and global climate models.

Organosulfates (OSs), with ambiguous formation mechanisms, are a potential source of "missing secondary organic aerosol (SOA)" in current atmospheric models. In this study, we analyzed the characterization and formation of OSs and nitrooxy OSs (NOSs) under the influence of biogenic emissions and anthropogenic pollutants (e.g. NOx, SO42−) in summer of Beijing. The ultrahigh-resolution mass spectrometer equipped with electrospray ionization source was applied to examine the overall molecular composition of S-containing organics. The number and intensities of S-containing organics, majority of which could be assigned as OSs and NOSs, increased significantly during pollution episodes, which indicated their importance for SOA accumulation. To further investigate the distribution and formation of OSs and NOSs, the high performance liquid chromatography coupled to mass spectrometer was then employed to quantify ten representative OSs and three NOS species. The total concentrations of quantified OSs and NOSs were 41.42 and 13.75 ng/m3, respectively. Glycolic acid sulfate was the most abundant species among all the quantified species, followed by monoterpene NOSs (C10H16NO7S−). The total concentration of three isoprene OSs was 14.77 ng/m3 and the isoprene OSs formed via HO2 channel was higher than those formed via NO/NO2 channel. The OS concentration coincided with the increase of acidic sulfate aerosols, aerosol acidity and liquid water content, indicating the acid-catalyzed aqueous-phase formation of OSs in the presence of acidic sulfate aerosols. When sulfate dominated the accumulation of secondary inorganic aerosols (SIAs) (SO42−/SIAs > 0.5), OS formation would be obviously promoted as the increasing of acidic sulfate aerosols, aerosol LWC and acidity (pH

Gasoline vehicles greatly contribute importantly to urban particulate matter (PM) pollution. Gasoline direct injection (GDI) engines, known as their higher fuel efficiency than that of port fuel injection (PFI) engines, have been increasingly employed in new gasoline vehicles. However, the impact of this trend on air quality is still poorly understood. Here, we investigated both primary emissions and secondary organic aerosol (SOA) formation from GDI and PFI vehicles under urban-like condition, using combined approaches involving chassis dynamometer measurement and environmental chamber simulation. The PFI vehicle emits slightly more volatile organic compounds, e.g., benzene and toluene, whereas the GDI vehicle emits more particulate components, e.g., the total PM, elemental carbon, primary organic aerosols and polycyclic aromatic hydrocarbons. Strikingly, a much higher SOA production (by a factor of approximately 2.7) is found from the exhaust of the GDI vehicle than that of the PFI vehicle under the same conditions. More importantly, the higher SOA production found in the GDI vehicle exhaust occurs concurrently with lower concentrations of traditional SOA precursors, e.g., benzene and toluene, indicating a greater contribution of intermediate volatility organic compounds and semivolatile organic compounds in the GDI vehicle exhaust to the SOA formation. Our results highlight the considerable potential contribution of GDI vehicles to urban air pollution in the future.

Gasoline vehicle exhaust is an important contributor to secondary organic aerosol (SOA) formation in urban atmosphere. Fuel composition has considerable potential impact on gasoline SOA production, but this impact is still taken little account in the emission regulations due to the poor understanding of the link between fuel components and SOA production. Here, we present an in-depth study to investigate the impact of gasoline aromatic content on SOA production through chamber approach. A significant amplification factor of 3–6 for SOA productions from gasoline exhausts was observed as gasoline aromatic content rose from 29 % to 37 %. Considerably higher emissions of aromatic volatile organic compounds performed an essential role in the SOA production enhancement. Our findings indicate that gasoline aromatics have significant influence on ambient PM2.5 concentration in megacities and highlight that more stringent regulation on gasoline aromatic content will achieve unexpected benefit on air quality in urban areas.

Highly time-resolved in-situ measurements of airborne particles were made at Mt. Yulong (3410 m above sea level) on the southeastern edge of the Tibetan Plateau in China from 20 March to 14 April in 2015. Detailed chemical composition was measured by a high-resolution time-of-flight aerosol mass spectrometer together with other online instruments. Average mass concentration of the submicron particles (PM1) was 5.7 ± 5.4 μg m−3 during the field campaign, ranging from 0.1 μg m−3 up to 33.3 μg m−3. Organic aerosol (OA) was the dominant component in PM1, with a fraction of 68 %. Three OA factors, i.e., biomass-burning organic aerosol (BBOA), biomass-burning-influenced oxygenated organic aerosol (OOA-BB) and oxygenated organic aerosol (OOA), were resolved using positive matrix factorization analysis. The two oxygenated OA factors accounted for 87 % of the total OA mass. Three biomass burning events were identified by examining the enhancement of black carbon concentrations and the f60 (the ratio of the signal at m/z 60 from the mass spectrum to the total signal of OA). Back trajectories of air masses and satellite fire map data were integrated to identify the biomass burning locations and pollutants transport. The western air mass from Southeast Asia with active biomass burning activities transported large amount of air pollutants, resulting in elevated organic concentrations up to 4-fold higher than that of the background condition. This study at Mt. Yulong characterizes the tropospheric background aerosols of the Tibetan Plateau during pre-monsoon season, and provides clear evidence that the southeastern edge of the Tibetan Plateau is affected by transport of anthropogenic aerosols from Southeast Asia.

As the world’s second largest economy, China has experienced severe haze pollution, with fine particulate matter (PM) recently reaching unprecedentedly high levels across many cities, and an understanding of the PM formation mechanism is critical in the development of efficient mediation policies to minimize its regional to global impacts. We demonstrate a periodic cycle of PM episodes in Beijing that is governed by meteorological conditions and characterized by two distinct aerosol formation processes of nucleation and growth, but with a small contribution from primary emissions and regional transport of particles. Nucleation consistently precedes a polluted period, producing a high number concentration of nano-sized particles under clean conditions. Accumulation of the particle mass concentration exceeding several hundred micrograms per cubic meter is accompanied by a continuous size growth from the nucleation-mode particles over multiple days to yield numerous larger particles, distinctive from the aerosol formation typically observed in other regions worldwide. The particle compositions in Beijing, on the other hand, exhibit a similarity to those commonly measured in many global areas, consistent with the chemical constituents dominated by secondary aerosol formation. Our results highlight that regulatory controls of gaseous emissions for volatile organic compounds and nitrogen oxides from local transportation and sulfur dioxide from regional industrial sources represent the key steps to reduce the urban PM level in China.

The photolysis frequency of NO2, j(NO2), is an important analytical parameter in the study of tropospheric chemistry. A chemical actinometer (CA) was built to measure the ambient j(NO2) based on a high precision NO x instrument with 1 min time resolution. Parallel measurements of the ambient j(NO2) by using the CA and a commercial spectroradiometer (SR) were conducted at a typical urban site (Peking University Urban Environmental Monitoring Station) in Beijing. In general, good agreement was achieved between the CA and SR data with a high linear correlation coefficient (R 2 = 0.977) and a regression slope of 1.12. The regression offset was negligible compared to the measured signal level. The j(NO2) data were calculated using the tropospheric ultraviolet visible radiation (TUV) model, which was constrained to observe aerosol optical properties. The calculated j(NO2) was intermediate between the results obtained with CA and SR, demonstrating the consistency of all the parameters observed at this site. The good agreement between the CA and SR data, and the consistency with the TUV model results, demonstrate the good performance of the installed SR instrument. Since a drift of the SR sensitivity is expected by the manufacturer, we propose a regular check of the data acquired via SR against those obtained by CA for long-term delivery of a high quality series of j(NO2) data. Establishing such a time series will be invaluable for analyzing the long-term atmospheric oxidation capacity trends as well as O3 pollution for urban Beijing.