Jianfei Peng

Elucidating severe urban haze formation in China

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. 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.

Persistent sulfate formation from London Fog to Chinese haze

Significance Exceedingly high levels of fine particulate matter (PM) occur frequently in China, but the mechanism of severe haze formation remains unclear. From atmospheric measurements in two Chinese megacities and laboratory experiments, we show that the oxidation of SO2 by NO2 occurs efficiently in aqueous media under two polluted conditions: first, during the formation of the 1952 London Fog via in-cloud oxidation; and second, on fine PM with NH3 neutralization during severe haze in China. We suggest that effective haze mitigation is achievable by intervening in the sulfate formation process with NH3 and NO2 emission control measures. Hence, our results explain the outstanding sulfur problem during the historic London Fog formation and elucidate the chemical mechanism of severe haze 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 SO2 by NO2 is key to efficient sulfate formation but is only feasible under two atmospheric conditions: on fine aerosols with high relative humidity and NH3 neutralization or under cloud conditions. Under polluted environments, this SO2 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 NH3 and NO2 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.

Markedly enhanced absorption and direct radiative forcing of black carbon under polluted urban environments

Significance Although black carbon (BC) represents a key short-lived climate forcer, its direct radiative forcing remains highly uncertain. The available results from available studies of absorption enhancement of BC particles during atmospheric aging are conflicting. Using a novel environmental chamber method, we have, for the first time to our knowledge, quantified the aging and variation in the optical properties of BC particles under ambient urban conditions representative of developed and developing countries. Our results indicate that BC under polluted urban environments could contribute significantly to both pollution development and large positive radiative forcing, implying that reduction of BC emissions under polluted environments achieves a cobenefit in simultaneously controlling air pollution and protecting climate, especially for developing countries. 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.

Chemical composition, sources, and aging process of submicron aerosols in Beijing: Contrast between summer and winter

To investigate the seasonal characteristics of submicron aerosol (PM1) in Beijing urban areas, a high-resolution time-of-flight aerosol-mass-spectrometer (HR-ToF-AMS) was utilized at an urban site in summer (August to September 2011) and winter (November to December 2010), coupled with multiple state of the art online instruments. The average mass concentrations of PM1 (60–84 µg m−3) and its chemical compositions in different campaigns of Beijing were relatively consistent in recent years. In summer, the daily variations of PM1 mass concentrations were stable and repeatable. Eighty-two percent of the PM1 mass concentration on average was composed of secondary species, where 62% is secondary inorganic aerosol and 20% secondary organic aerosol (SOA). In winter, PM1 mass concentrations changed dramatically because of the different meteorological conditions. The high average fraction (58%) of primary species in PM1 including primary organic aerosol (POA), black carbon, and chloride indicates primary emissions usually played a more important role in the winter. However, aqueous chemistry resulting in efficient secondary formation during occasional periods with high relative humidity may also contribute substantially to haze in winter. Results of past OA source apportionment studies in Beijing show 45–67% of OA in summer and 22–50% of OA in winter can be composed of SOA. Based on the source apportionment results, we found 45% POA in winter and 61% POA in summer are from nonfossil sources, contributed by cooking OA in both seasons and biomass burning OA (BBOA) in winter. Cooking OA, accounting for 13–24% of OA, is an important nonfossil carbon source in all years of Beijing and should not be neglected. The fossil sources of POA include hydrocarbon-like OA from vehicle emissions in both seasons and coal combustion OA (CCOA) in winter. The CCOA and BBOA were the two main contributors (57% of OA) for the highest OA concentrations (>100 µg m−3) in winter. The POA/ΔCO ratios in winter and summer are 11 and 16 µg m−3 ppm−1, respectively, similar to ratios from western cities. Higher OOA/Ox (= NO2 + O3) ratio (0.49 µg m−3 ppb−1) in winter study than these ratios from western cities (0.03–0.16 µg m−3 ppb−1) was observed, which may be due to the aqueous reaction or extra SOA formation contributed by semivolatile organic compounds from various primary sources (e.g., BBOA or CCOA) in Beijing. The evolution of oxygen to carbon ratio (O/C) with photochemical age allows to estimate an equivalent rate constant for chemical aging of OA in summer as kOH ~ 4.1 × 10−12 cm3 molecule−1 s−1, which is of the same order as obtained in other anthropogenic influenced areas and may be useful for OA modeling.

Estimation of size-resolved ambient particle density based on the measurement of aerosol number, mass, and chemical size distributions in the winter in Beijing.

Simultaneous measurements of aerosol size, distribution of number, mass, and chemical compositions were conducted in the winter of 2007 in Beijing using a Twin Differential Mobility Particle Sizer and a Micro Orifice Uniform Deposit Impactor. Both material density and effective density of ambient particles were estimated to be 1.61 ± 0.13 g cm(-3) and 1.62 ± 0.38 g cm(-3) for PM(1.8) and 1.73 ± 0.14 g cm(-3) and 1.67 ± 0.37 g cm(-3) for PM(10). Effective density decreased in the nighttime, indicating the primary particles emission from coal burning influenced the density of ambient particles. Size-resolved material density and effective density showed that both values increased with diameter from about 1.5 g cm(-3) at the size of 0.1 μm to above 2.0 g cm(-3) in the coarse mode. Material density was significantly higher for particles between 0.56 and 1.8 μm during clean episodes. Dynamic Shape Factors varied within the range of 0.95-1.13 and decreased with particle size, indicating that coagulation and atmospheric aging processes may change the shape of particles.

Spatial distributions and chemical properties of PM2.5 based on 21 field campaigns at 17 sites in China.

Severe air pollution and its associated health impacts have become one of the major concerns in China. A detailed analysis of PM2.5 chemical compositions is critical for optimizing pollution control measures. In this study, daily 24-h bulk filter samples were collected and analyzed for totally 21 field campaigns at 17 sites in China between 2008 and 2013. The 17 sites were classified into four groups including six urban sites, seven regional sites, two coastal sites in four fast developing regions of China (i.e. Beijing-Tianjin-Hebei region, Yangtze River Delta, Pearl River Delta and Sichuan Basin), and two ship cruise measurements covered the East China Sea and Yellow Sea of China. The high average concentrations of PM2.5 and the occurrences of extreme cases at most sites imply the widespread air pollution in China. Fine particles were largely composed of organic matter and secondary inorganic species at most sites. High correlation between the temporal trends of PM2.5 and secondary species of urban and regional sites highlights the uniformly distributed air pollutants within one region. Secondary inorganic species were the dominant contributors to the high PM2.5 concentration in Northern China. However in Southern China, the relative contributions of different chemical species kept constant as PM2.5 increased. This study provides us a better understanding of the current state of air pollution in diversified Chinese cities. Analysis of chemical signatures of PM2.5 could be a strong support for model validation and emission control strategy.

OH-Initiated Oxidation of m-Xylene on Black Carbon Aging.

Laboratory experiments are conducted to investigate aging of size-classified black carbon (BC) particles from OH-initiated oxidation of m-xylene. The variations in the particle size, mass, effective density, morphology, optical properties, hygroscopicity, and activation as cloud condensation nuclei (CCN) are simultaneously measured by a suite of aerosol instruments, when BC particles are exposed to the oxidation products of the OH-m-xylene reactions. The BC aging is governed by the coating thickness (Δrve), which is correlated to the reaction time and initial concentrations of m-xylene and NOx. For an initial diameter of 100 nm and Δrve = 44 nm, the particle size and mass increase by a factor of 1.5 and 10.4, respectively, and the effective density increases from 0.43 to 1.45 g cm(-3) due to organic coating and collapsing of the BC core. The BC particles are fully converted from a highly fractal to nearly spherical morphology for Δrve = 30 nm. The scattering, absorption, and single scattering albedo of BC particles are enhanced accordingly with organic coating. The critical supersaturation for CCN activation is reduced to 0.1% with Δrve = 44 nm. The results imply that the oxidation of m-xylene exhibits larger impacts in modifying the BC particle properties than those for the OH-initiated oxidation of isoprene and toluene.

Reassessing the atmospheric oxidation mechanism of toluene

Significance Aromatic hydrocarbons account for 20 to 30% of volatile organic compounds and contribute importantly to ozone and secondary organic aerosol (SOA) formation in urban environments. The oxidation of toluene, the most abundant aromatic compound, is believed to occur mainly via OH addition, primary organic peroxy radical (RO2) formation, and ring cleavage, leading to ozone and SOA. From combined experimental and theoretical studies, we show that cresol formation is dominant, while primary RO2 production is negligible. Our work reveals that the formation and subsequent reactions of cresols regulate the atmospheric impacts of toluene oxidation, suggesting that its representation in current atmospheric models should be reassessed for accurate determination of ozone and SOA formation. The results from our study provide important constraints and guidance for future modeling studies. Photochemical oxidation of aromatic hydrocarbons leads to tropospheric ozone and secondary organic aerosol (SOA) formation, with profound implications for air quality, human health, and climate. Toluene is the most abundant aromatic compound under urban environments, but its detailed chemical oxidation mechanism remains uncertain. From combined laboratory experiments and quantum chemical calculations, we show a toluene oxidation mechanism that is different from the one adopted in current atmospheric models. Our experimental work indicates a larger-than-expected branching ratio for cresols, but a negligible formation of ring-opening products (e.g., methylglyoxal). Quantum chemical calculations also demonstrate that cresols are much more stable than their corresponding peroxy radicals, and, for the most favorable OH (ortho) addition, the pathway of H extraction by O2 to form the cresol proceeds with a smaller barrier than O2 addition to form the peroxy radical. Our results reveal that phenolic (rather than peroxy radical) formation represents the dominant pathway for toluene oxidation, highlighting the necessity to reassess its role in ozone and SOA formation in the atmosphere.

Aging and hygroscopicity variation of black carbon particles in Beijing measured by a quasi-atmospheric aerosol evolution study (QUALITY) chamber

Measurements of ageing and hygroscopicity variation of black carbon (BC) particles in Beijing were conducted using a 1.2 m3 quasi-atmospheric aerosol evolution study (QUALITY) chamber, which consisted of a bottom flow chamber through which ambient air was pulled continuously and an upper reaction chamber where ageing of BC particles occurred. Within the reaction chamber, transmission of the solar ultraviolet irradiation was approximately 50–60 %, wall loss of primary gaseous pollutants was negligible, and BC exhibited a half-lifetime of about 3–7 h. Typically, equilibrium for the primary gases, temperature and relative humidity between the reaction chamber and ambient air was established within 1 h. Rapid growth of BC particles occurred, with an average total growth of 77± 33 nm and average growth rate of 26± 11 nm h−1. Secondary organic aerosols (SOA) accounted for more than 90 % of the coating mass. The O /C ratio of SOA was 0.5, lower than the ambient level. The hygroscopic growth factor of BC particles decreased slightly with an initial thin coating layer because of BC reconstruction, but subsequently increased to 1.06–1.08 upon further ageing. The κ (kappa) values for BC particles and coating materials were calculated as 0.035 and 0.040 at the subsaturation and supersaturation conditions, respectively, indicating low hygroscopicity of coated SOA on BC particles. Hence, our results indicate that initial photochemical ageing of BC particles leads to considerable modifications to morphology and optical properties but does not appreciably alter the particle hygroscopicity in Beijing.

Characterization of particle number size distribution and new particle formation in Southern China

Knowledge of particle number size distribution (PND) and new particle formation (NPF) events in Southern China is essential for mitigation strategies related to submicron particles and their effects on regional air quality, haze, and human health. In this study, seven field measurement campaigns were conducted from December 2013 to May 2015 using a scanning mobility particle sizer (SMPS) at four sites in Southern China, including three urban sites and one background site. Particles were measured in the size range of 15-615nm, and the median particle number concentrations (PNCs) were found to vary in the range of 0.3×104-2.2×104cm-3 at the urban sites and were approximately 0.2×104cm-3 at the background site. The peak diameters at the different sites varied largely from 22 to 102nm. The PNCs in the Aitken mode (25-100nm) at the urban sites were up to 10 times higher than they were at the background site, indicating large primary emissions from traffic at the urban sites. The diurnal variations of PNCs were significantly influenced by both rush hour traffic at the urban sites and NPF events. The frequencies of NPF events at the different sites were 0%-30%, with the highest frequency occurring at an urban site during autumn. With higher SO2 concentrations and higher ambient temperatures being necessary, NPF at the urban site was found to be more influenced by atmospheric oxidizing capability, while NPF at the background site was limited by the condensation sink. This study provides a unique dataset of particle number and size information in various environments in Southern China, which can help understand the sources, formation, and the climate forcing of aerosols in this quickly developing region, as well as help constrain and validate NPF modeling.