Significance We illustrate the similarity and difference in particulate matter (PM) formation between Beijing and other world regions. The periodic cycle of PM events in Beijing is regulated by meteorological conditions. While the particle chemical compositions in Beijing are similar to those commonly measured worldwide, efficient nucleation and growth over an extended period in Beijing are distinctive from the aerosol formation typically observed in other global areas. Gaseous emissions of volatile organic compounds and nitrogen oxides from urban transportation and sulfur dioxide from regional industry are responsible for large secondary PM formation, while primary emissions and regional transport of PM are insignificant. Reductions in emissions of the aerosol precursor gases from transportation and industry are essential to mediate severe haze pollution in China.

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.sulfate aerosol | severe haze | pollution | human health | climate

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.black carbon | absorption | air quality | radiative forcing | climate B lack carbon (BC) particles, produced from incomplete fossil fuel combustion and biomass burning, are ubiquitous in the atmosphere and have profound impacts on air quality and climate (1-4). As a key short-lived climate forcer, the magnitude of BC direct radiative forcing (DRF) is dependent on the mixing state, i.e., whether particles are externally or internally mixed with other aerosol types (5, 6), and atmospheric aging by coating with secondary aerosol constituents (such as organics and sulfate) enhances the mass absorption cross-section (MAC) (5-9). Previous laboratory studies conducted under controlled experimental conditions yielded a broad range of MAC enhancements from 1.05 to 3.50, varying with the diameter, morphology, and coating of BC particles (7-15). On the other hand, a field measurement indicated a negligible absorption enhancement of ambient BC particles under a variable mixing state (16). In addition, BC aging and absorption enhancement also strongly impact visibility and atmospheric stability.Few direct measurements have been conducted to capture aging and quantify the related absorption variation of BC particles under ambient conditions. In particular, atmospheric measurements at fixed sites are affected by transport, local emissions, and chemistry, and quantification of the evolution in the BC properties (such as morphology, mixing state, and absorption and scattering coefficients) during aging involves complex decoupli...

31°N approximately). In addition, major drought/flood events considering severity, persistency, and spatial coverage were also identified. On the centennial time scales, precipitation variation in eastern China exhibited four dry epochs (500s -870s, 1000s -1230s, 1430s -1530s and 1920s -1990s) and three wet epochs (880s -990s, 1240s -1420s and 1540s -1910s), with multi-decadal dry/wet fluctuations within each epoch. However, variation showed strong regional differences, for example, opposite trends were found in the Jiang-Nan area and Jiang-Huai area during the 11 -13th centuries and in the North China Plain and JiangNan area since the 16th century. The data also showed 16 drought and 18 flood events in eastern China, with the most severe drought event occurring in 1634 -1644. Droughts dominated in the 12 -14th centuries, but since the middle of the17th century eastern China has been more subject to flooding. The severity of floods during the 20th century was comparable in intensity to historical times, but the droughts were usually less severe.

Phenological cold/warm events recorded in Chinese historical documents are used to reconstruct, at 10-30 years' resolution, winter half-year (October to April) temperatures for the past 2000 years in the central region of eastern China. Because of the uneven spatial and temporal distribution of the phenological records, the reconstruction of the regional mean temperature involves two steps: reconstruction for individual sites within the region and calculation of the regional mean. For a single site, the reconstruction involves: identifying the difference in dates in phenological events for both historical and modern records; establishing the conversion function between the date difference and temperature change from the modern records; and converting the historical records into temperature variation. The spatial representativeness of the individual sites is studied by examining the correlation between individual sites and regional mean temperature from modern instrumental data. The correlation is then used as the basis for constructing the regional mean winter half-year temperature for the past 2000 years. From the beginning of the Christian era, climate became cooler at a rate of 0.17°C per century, and around the ad 490s temperature reached about 1°C lower than that of the present (the 1951-80 mean). Then, abruptly, temperature entered a warm epoch from the ad 570s to 1310s with a warming trend of 0.04°C per century; the peak warming was about 0.3-0.6°C higher than present for 30-year periods, but over 0.9°C warmer on a 10-year basis. After the ad 1310s, temperature decreased rapidly at a rate of 0.10°C per century; the mean temperatures of the four cold troughs were 0.6-0.9°C lower than the present, with the coldest value 1.1°C lower. Temperature has been rising rapidly during the twentieth century, especially for the period 1981-99, and the mean temperature is now 0.5°C higher than for 1951-80. The most interesting aspect over the past 2000 years has been the rapid transitions between cold and warm periods.

The particle phase state is a key factor for determining gas particle partitioning, particle reactive gas uptake, and multiphase chemical reactions, with associated links to secondary aerosol formation. In this study, the particle phase state was investigated by measuring particle rebound fraction f in the highly polluted atmosphere of Beijing, China. The particle phase state was sensitive to ambient relative humidity (RH). The particles changed from rebounding to adhering when the RH increased above 60%, suggesting a transition from the semisolid to liquid state. This transition RH was below the deliquescence RH of both (NH4)2SO4 and NH4NO3. Submicrometer particles were in the liquid state during heavy haze episodes. This might be because the elevated RH and inorganic fraction in particles resulted in an increase in aerosol liquid water content. The transition to a liquid phase state, marking the beginning of the haze episode, might kick off a positive feedback loop. The liquid particles might readily take up pollutants that then react to form inorganics, thereby further increasing the rate of water uptake. We propose that the liquid phase state facilitates the mass transfer and multiphase reactions of the particles, thereby accelerating secondary particle growth in haze over the North China Plain.

Abstract. 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 NO3- concentrations and (NO3-)/NACs ratios were lower, implying organic-dominated products. Under high-NOx conditions, NAC concentrations did not further increase with NO2, while the NO3- concentrations and (NO3-)/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.

Abstract. A severe regional haze problem in the megacity Beijing and surrounding areas, caused by fast formation and growth of fine particles, has attracted much attention in recent years. In order to investigate the secondary formation and aging process of urban aerosols, four intensive campaigns were conducted in four seasons between March 2012 and March 2013 at an urban site in Beijing (116.31 • E, 37.99 • N). An Aerodyne highresolution time-of-flight aerosol mass spectrometry (HRToF-AMS) was deployed to measure non-refractory chemical components of submicron particulate matter (NR-PM 1 ). The average mass concentrations of PM 1 (NR-PM 1 +black carbon) were 45.1 ± 45.8, 37.5 ± 31.0, 41.3 ± 42.7, and 81.7 ± 72.4 µg m −3 in spring, summer, autumn, and winter, respectively. Organic aerosol (OA) was the most abundant component in PM 1 , accounting for 31, 33, 44, and 36 % seasonally, and secondary inorganic aerosol (SNA, sum of sulfate, nitrate, and ammonium) accounted for 59, 57, 43, and 55 % of PM 1 correspondingly. Based on the application of positive matrix factorization (PMF), the sources of OA were obtained, including the primary ones of hydrocarbonlike (HOA), cooking (COA), biomass burning OA (BBOA) and coal combustion OA (CCOA), and secondary component oxygenated OA (OOA). OOA, which can be split into moreoxidized (MO-OOA) and less-oxidized OOA (LO-OOA), accounted for 49, 69, 47, and 50 % in four seasons, respectively. Totally, the fraction of secondary components (OOA+SNA) contributed about 60-80 % to PM 1 , suggesting that secondary formation played an important role in the PM pollution in Beijing, and primary sources were also non-negligible. The evolution process of OA in different seasons was investigated with multiple metrics and tools. The average carbon oxidation states and other metrics show that the oxidation state of OA was the highest in summer, probably due to both strong photochemical and aqueousphase oxidations. It was indicated by the good correlations (r = 0.53-0.75, p < 0.01) between LO-OOA and odd oxygen (O x = O 3 + NO 2 ), and between MO-OOA and liquid water content in aerosols. BBOA was resolved in spring and autumn, influenced by agricultural biomass burning (e.g., field preparation burnings, straw burning after the harvest). CCOA was only identified in winter due to domestic heating. These results signified that the comprehensive management for biomass burning and coal combustion emissions is needed. High concentrations of chemical components in PM 1 in Beijing, especially in winter or in adverse meteorological conditions, suggest that further strengthening the regional emission control of primary particulate and precursors of secondary species is expected.