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 alpha-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 alpha-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 alpha-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 alpha-dicarbonyls and amines. BrC aerosols, if formed from the particle-phase reaction of methylglyoxal with methylamine, likely contribute to atmospheric warming.
Nitryl chloride (ClNO2) accumulation at night acts as a significant reservoir for active chlorine and impacts the following day's photochemistry when the chlorine atom is liberated at sunrise. Here, we report simultaneous measurements of N2O5 and a suite of inorganic halogens including ClNO2 and reactions of chloride with volatile organic compounds (Cl-VOCs) in the gas and particle phases utilising the Filter Inlet for Gas and AEROsols time-of-flight chemical ionisation mass spectrometer (FIGAERO-ToF-CIMS) during an intensive measurement campaign 40 km northwest of Beijing in May and June 2016. A maximum mixing ratio of 2900 ppt of ClNO2 was observed with a mean campaign nighttime mixing ratio of 487 ppt, appearing to have an anthropogenic source supported by correlation with SO2, CO and benzene, which often persisted at high levels after sunrise until midday. This was attributed to such high mixing ratios persisting after numerous e-folding times of the photolytic lifetime enabling the chlorine atom production to reach 2.3 x 10(5) molecules cm(-3) from ClNO2 alone, peaking at 09:30 LT and up to 8.4 x 10(5) molecules cm(-3) when including the supporting inorganic halogen measurements.Cl-VOCs were observed in the particle and gas phases for the first time at high time resolution and illustrate how the iodide ToF-CIMS can detect unique markers of chlorine atom chemistry in ambient air from both biogenic and anthropogenic sources. Their presence and abundance can be explained via time series of their measured and steady-state calculated precursors, enabling the assessment of competing OH and chlorine atom oxidation via measurements of products from both of these mechanisms and their relative contribution to secondary organic aerosol (SOA) formation.
Biomass burning (BB) activities have a great impact on the particle number size distribution (PNSD) in the upper troposphere of the Tibetan Plateau, which could affect regional and global climate. An intensive campaign focused on the measurement of the PNSD, gaseous pollutants, and meteorological parameters was conducted at Mt. Yulong, a high-altitude site (3410ma.s.l.) on the southeastern Tibetan Plateau during the pre-monsoon season (22 March to 15 April). During this period, intensive BB activities in southern Asia were detected by fire maps. The long-range transport of BB pollutants can increase the accumulation mode particles in the background atmosphere at Mt. Yulong. As a consequence, the cloud condensation nuclei (CCN) concentration was found to be 2-8 times higher during BB periods than during clean periods. Apart from BB, variations of the planet boundary layer (PBL) and new particle formation (NPF) were other factors that influenced the PNSD. However, only three NPF events (with a frequency of 14 %) were observed at Mt. Yulong. The occurrence of NPF events during clean episodes corresponded to an elevated PBL or transported BB pollutants. Due to the lack of condensable vapors including sulfuric acid and organic compounds, the newly formed particles were not able to grow to CCN size. Our study emphasizes the influences of BB on the aerosol and CCN concentration in the atmosphere of the Tibetan Plateau. These results also have the potential to improve our understanding of the variation of the particle concentration in the upper troposphere, and provide information for regional and global climate models.
With the rapid economic development and urbanization of China, haze and photochemical smog events have been frequently observed during the last decade. To explore the temporal and spatial pollution characteristics in Ningbo, a medium-sized coastal city located in the Yangtze River Delta (YRD) in southeast China, 24-h PM2.5 (particulate matter with aerodynamic diameter < 2.5 mu m) samples were simultaneously collected at five sites (two urban residential sites, two urban coastal sites, and one suburban site) from winter 2012 to autumn 2013. The average PM2.5 concentration was 53.2 +/- 30.4 mu g m(-3). Furthermore, the concentration exhibited a seasonal variation: It was highest in winter and lowest in summer. The urban residential sites had the highest PM2.5 concentrations, followed by the urban coastal sites, and the suburban site had the lowest concentration. OM (Organic Matters) and secondary inorganic ions (sulfate, nitrate, and ammonium) were the dominant components of the PM2.5. As a coastal city with industrial zones, sources are more complex in Ningbo than in inland cities due to ship emissions and the interactions between land and sea, and the marine and atmospheric environments. Positive matrix factorization (PMF) was used to apportion the particle sources. Nine factors were resolved in this study: secondary nitrate, vehicle exhaust, secondary sulfate, coal combustion, industrial emission, ship emission, dust, biomass burning, and aged sea salt, with average contributions of 26%, 21%, 13%, 12%, 9%, 7%, 5%, 4%, and 3%, respectively. Secondary nitrate and vehicle exhaust were the major sources of PM2.5 pollution in Ningbo. Coal combustion contributed significantly in winter and autumn, whereas sea salt formed a considerable contribution in summer. This study suggests that decreasing the PM2.5 pollution in Ningbo requires not only strategies for reducing local primary sources but also joint inter-regional prevention and the control of air pollution in the YRD.
This study reveals aerosol liquid water content (ALWC) in PM2.5 ranged from 2% up to 74%, and the associated secondary inorganic fraction rose from 24% to 55%, while ambient relative humidity (RH) increased from 15% to 83% in the atmosphere over Beijing. Unexpectedly, the secondary inorganic fraction in PM2.5 increased with an increase in the ambient RH, which is a meteorological parameter independent of anthropogenic activities, indicating the presence of a feedback mechanism driven by Henry's law and thermodynamic equilibrium. During haze episodes, simultaneously elevated RH levels and anthropogenic secondary inorganic mass concentrations resulted in an abundant ALWC. The condensed water could act as an efficient medium for multiphase reactions, thereby facilitating the transformation of reactive gaseous pollutants into particles and accelerating the formation of heavy haze. ALWC was well correlated with the mass concentrations of both nitrate and sulfate, indicating both nitrate and sulfate salts play key roles in determining ALWC. Coincident with a significant reduction in SO2 emissions throughout China, nitrates will become a dominant anthropogenic inorganic salt driving ALWC. Thus, the abundance of ALWC and its effects on the aerosol chemistry and climate should be reconsidered.
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. (C) 2017 The Research Center for Eco-Environmental Sciences, Chinese Academy of Sciences. Published by Elsevier B.V.
Particle density is an important physical property of atmospheric particles. The information on high time-resolution size-resolved particle density is essential for understanding the atmospheric physical and chemical aging processes of aerosols particles. In the present study, a centrifugal particle mass analyzer (CPMA) combined with a differential mobility analyzer (DMA) was deployed to determine the size-resolved effective density of 50 to 350nm particles at a rural site of Beijing during summer 2016. The measured particle effective densities decreased with increasing particle sizes and ranged from 1.43 to 1.55g/cm3, on average. The effective particle density distributions were dominated by a mode peaked at around 1.5g/cm3 for 50 to 350nm particles. Extra modes with peaks at 1.0, 0.8, and 0.6g/cm3 for 150, 240, and 350nm particles, which might be freshly emitted soot particles, were observed during intensive primary emissions episodes. The particle effective densities showed a diurnal variation pattern, with higher values during daytime. A case study showed that the effective density of Aitken mode particles during the new particle formation (NPF) event decreased considerably, indicating the significant contribution of organics to new particle growth.
Gasoline vehicle exhaust is an important contributor to secondary organic aerosol (SOA) formation in urban atmosphere. Fuel composition has a potentially considerable impact on gasoline SOA production, but the link between fuel components and SOA production is still poorly understood. Here, we present chamber experiments to investigate the impacts of gasoline aromatic content on SOA production through chamber oxidation approach. A significant amplification factor of 3-6 for SOA productions from gasoline exhausts is observed as gasoline aromatic content rose from 29 to 37 %. Considerably higher emission of aromatic volatile organic compounds (VOCs) using high-aromatic fuel plays an essential role in the enhancement of SOA production, while semi-volatile organic compounds (e.g., gas-phase PAHs) may also contribute to the higher SOA production. Our findings indicate that gasoline aromatics significantly influence ambient PM2.5 concentration in urban areas and emphasize that more stringent regulation of gasoline aromatic content will lead to considerable benefits for urban air quality.
Particulate organonitrates are formed from volatile organic compounds (VOCs) oxidation by radicals. A portion of semi-volatile gas-phase organonitrates can be incorporate into aerosol by oxidation reactions or portioning, and has been an important component of secondary organic aerosol (SOA). Particulate organonitrates study has become one of the important aspects of atmospheric chemistry. Given the large number and variability of chemical constituents, and possible chemical transformations of organonitrates, such characterization presents a key problem for research. Based on recent research progress on particulate organonitrates, this paper summarizes the formation mechanism and quantification method of particulate organonitrates. Profiting from the application of high time resolution techniques, field measurements has become the major approach of particulate organonitrates study. Thermal dissociation-laser induced fluorescence (TD-LIF) and aerosol mass spectrometers (AMS) have been used to quantify and provide the evolution processes of particulate organonirates. Meanwhile, chemical ionization mass spectrometer(CIMS)allows for the determination of molecular ion composition of organonitrates, promising to become the important direction of study of particulate organonirates in future field measurements. To have a deep insight on precursor and atmospheric chemistry processes of particulate organonirates, future research should focus on the combination of field measurement, modeling simulation and laboratory simulation, and these will also lead to a more comprehensive understanding of formation mechanism of particulate organonirates
Although organic compounds in marine atmospheric aerosols have significant effects on climate and marine ecosystems, they have rarely been studied, especially in the coastal regions of East China. To assess the origins of the organic aerosols in the East China coastal atmosphere, PM2.5 samples were collected from the atmospheres of the Yellow Sea, the East China Sea, and Changdao Island during the CAPTAIN (Campaign of Air PolluTion At INshore Areas of Eastern China) field campaign in the spring of 2011. The marine atmospheric aerosol samples that were collected were grouped based on the backward trajectories of their air masses. The organic carbon concentrations in the PM2,5 samples from the marine and Changdao Island atmospheres were 5.5 +/- 3.1 mu gC/m(3) and 6.9 +/- 2.4 mu gC/m(3), respectively, which is higher than in other coastal water atmospheres. The concentration of polycyclic aromatic hydrocarbons (PAHs) in the marine atmospheric PM2.5 samples was 17.0 +/- 20.2 ng/m(3), indicating significant continental anthropogenic influences. The influences of fossil fuels and biomass burning on the composition of organic aerosols in the coastal atmosphere of East China were found to be highly dependent on the origins of the air masses. Diesel combustion had a strong impact on air masses from the Yangtze River Delta (YRD), and gasoline emissions had a more significant impact on the "North China" marine atmospheric samples. The "Northeast China" marine atmospheric samples were most impacted by biomass burning. Coal combustion contributed significantly to the compositions of all of the atmospheric samples. The proportions of secondary compounds increased as samples aged in the marine atmosphere indicating that photochemical oxidation occured during transport. Our results quantified ecosystem effects on marine atmospheric aerosols and highlighted the uncertainties that arise when modeling marine atmospheric PM2.5 without considering high spatial resolution source data and meteorological parameters. (C) 2017 Published by Elsevier Ltd.