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.
The heterogeneous hydrolysis of dinitrogen pentoxide (N2O5) is important to understanding the formation of particulate nitrate (pNO(3)(-)). Measurements of N2O5 in the surface layer taken at an urban site in Beijing are presented here. N2O5 was observed with large day-to-day variability. High N2O5 concentrations were determined during pollution episodes with the co-presence of large aerosol loads. The maximum value was 1.3 ppbv (5 s average), associated with an air mass characterized by a high level of O-3. N2O5 uptake coefficients were estimated to be in the range of 0.025-0.072 using the steady-state lifetime method. As a consequence, the nocturnal pNO(3)(-) formation potential by N2O5 heterogeneous uptake was calculated to be 24-85 mu g m(-3) per night and, on average, 57 mu g m(-3) during days with pollution. This was comparable to or even higher than that formed by the partitioning of HNO3. The results highlight that N2O5 heterogeneous hydrolysis is vital in pNO(3)(-) formation in Beijing.
The molecular composition of humic-like [GRAPHIC] substances (HULIS) in different aerosol samples was analyzed using an ultrahigh-resolution mass spectrometer to investigate the influence of biomass burning on ambient aerosol composition. HULIS in background aerosols were characterized with numerous molecular formulas similar to biogenic secondary organic aerosols. The abundance of nitrogen-containing organic compounds (NOC), including nitrogen-containing bases (N-bases) and nitroaromatics, increased dramatically in ambient aerosols affected by crop residue burning in the farm field. The molecular distribution of N-bases in these samples exhibited similar patterns to those observed in smoke particles freshly emitted from lab-controlled burning of straw residues but were significantly different with those observed from wood burning. Signal intensity of the major N-bases correlated well with the atmospheric concentrations of potassium and levoglucosan. These N-bases can serve as molecular markers distinguishing HULIS from crop residue burning with from wood burning. More nitroaromatics were detected in ambient aerosols affected by straw burning than in fresh smoke aerosols, indicating that many of them are formed in secondary oxidation processes as smoke plumes evolve in the atmosphere. This study highlights the significant contribution of crop residue burning to atmospheric NOC. Further study is warranted to evaluate the roles of NOC on climate and human health.
Long-term measurements of particle number size distributions in combination with thermodenuder analysis have been performed since July 2003 at the Central European station of Melpitz, Germany. Up to the end of 2011, 20% of all investigated days during the 8.5 years of measurements showed new particle formation and subsequent growth. To investigate the role of various chemical compound candidates for condensational nanoparticle growth, we focused on nucleation events in which the measured size distributions with and without thermodesorption both showed growth patterns (accounting for up to similar to 85% of all nucleation events). In this study, particulate compounds that volatilize at 300 degrees C were specifically defined as "volatile," in contrast to "nonvolatile" compounds, which remain in the particulate phase after being heated to 300 degrees C. A strong correlation between ambient temperature and growth rate associated with volatile substances (except gaseous sulfuric acid) was found, which implies the importance of organics (possibly oxidized biogenic organic compounds) in particle growth at Melpitz. The contributions of the volatile compounds to the growth rate due to condensation of gaseous sulfuric acid and organics were found to be about 19% and 47%, respectively. The remaining similar to 25% was attributed to nonvolatile residuals, which appear to form gradually during the particle growth process and are characterized as extremely low-volatility compounds. The growth rate associated with volatile components exhibited significant seasonal variation, with the highest value during summertime, whereas the growth rate associated with the nonvolatile fraction showed less fluctuation.
New particle formation (NPF) studies have been conducted in China since 2004. Formation of new atmospheric aerosol particles has been observed to take place in diverse environments, even under the circumstances of high pre-existing particle loading, challenging the traditional and present understanding of the physicochemical nucleation mechanisms, which have been proposed based on the investigations in clean environments and under laboratory experimental conditions. This paper summarizes the present status and gaps in understanding NPF in China and discusses the main directions opening for future research. (C) 2016 Elsevier B.V. All rights reserved.
Atmospheric new particle formation and growth play important roles in climate change and air quality. Aiming at better understanding the particle growth mechanisms, the measurements on chemical composition of new particles are imperative. However, the instruments directly detecting chemical composition of nanoparticles (<30 nm) are very rare due to the tiny particle masses involved and low transmission efficiency. Alternatively, the hygroscopicity and volatility of nanoparticles were measured to infer chemical composition of the particle. Here, we summarized the progresses in studying the new particle growth processes on a basis of particle hygroscopicity and volatility measurements. Compared to clean environments, such as in boreal forest, the water soluble components contribute a larger fraction of newly formed particles (below 50 nm) in the polluted environments, such as in the sulfur-rich atmosphere of North China Plain. The extreme low volatility components in new particles were observed in both clean and polluted environments and contributed to 1/4 of particle growth in a rural site of Melpitz, Germany. In the future, the instruments capable of precisely detecting the hygroscopicity and volatility of particles below 10 nm are needed. Except for differential mobility analyzer, other novel methods without limitation of charging and transmission efficiency should be considered. The hygroscopicity and volatility of atmospheric relevant compounds should be investigated in the laboratory in order to provide supportive information to explain the hygroscopicity and volatility of new particle in the ambient air.
To better understand the sources, formation, and the transport of air pollutants over North China Plain (NCP), a four-week intensive campaign during summertime in 2014 was conducted in a central NCP rural site. In this study, particle hygroscopicity and volatility measurements were focused to characterize the thermodynamic properties of nanoparticles and gain insight into chemical composition of nanoparticles during the new particle formation (NPF) events. The water-soluble fractions of 30 and 50 nm newly formed particles were respectively 0.64 +/- 0.06 and 0.61 +/- 0.06, indicating that the water-soluble chemical compounds, most likely ammonium sulfate, dominated the condensational growth of newly formed particles over the NCP. Due to containing higher water-soluble fraction, nanoparticles can be activated as cloud condensation nuclei (CCN) at lower supersaturation in the atmosphere of NCP in contrast to cleaner environments, such as Melpitz (Central European background) and Hyytiala (boreal forest) during the NPF events. Our observations showed that the NPF and subsequent growth significantly resulted in an enhancement in CCN number concentration. The ranges of enhancement factors of CCN number concentration for supersaturation (SS) = 0.2, 0.4, 0.8% were respectively 1.9-7.0, 2.7-8.4, and 3.6-10.1. After being heated to 300 degrees C, the shrink factors for 30 and 50 nm particles were respectively 0.35 and 038. This indicated that non-volatile compounds could be produced during the growth process of newly formed particles. (C) 2017 Elsevier B.V. All rights reserved.
Biomass burning emits large amounts of both trace gases and particles into the atmosphere. It plays a profound role in regional air quality and climate change. In the present study, an intensive campaign was carried out at an urban site in Beijing, China, in June 2014, which covered the winter wheat harvest season over the North China Plain (NCP). Meanwhile, two evident biomass-burning events were observed. A clear burst in ultrafine particles (below 100 nm in diameter, PM1) and subsequent particle growth took place during the events. With the growth of the ultrafine particles, the organic fraction of PM1 increased significantly. The ratio of oxygen to carbon (O:C), which had an average value of 0.23 +/- 0.04, did not show an obvious enhancement, indicating that a significant chemical aging process of the biomass-burning aerosols was not observed during the course of events. This finding might have been due to the fact that the biomass-burning events occurred in the late afternoon and grewduring the nighttime, which is associated with a low atmospheric oxidation capacity. On average, organics and black carbon (BC) were dominant in the biomass-burning aerosols, accounting for 60 +/- 10% and 18 +/- 3% of PM1. The high organic and BC fractions led to a significant suppression of particle hygroscopicity. Comparisons among hygroscopicity tandem differential mobility analyzer (HTDMA)-derived, cloud condensation nuclei counter (CCNc)-derived, and aerosol mass spectrometer-based hygroscopicity parameter (kappa) values were consistent. The mean. values of biomass-burning aerosols derived from both HTDMA and CCNc measurements were approximately 0.1, regardless of the particle size, indicating that the biomass-burning aerosols were less active. The burst in particle count during the biomass-burning events resulted in an increased number of cloud condensation nuclei (CCN) at supersaturation (SS)= 0.2-0.8%. (C) 2016 Elsevier B.V. All rights reserved.
East Asia is a densely populated region with a myriad of primary emissions of pollutants such as black carbon (BC) and carbon monoxide (CO). To characterize primary emissions over the eastern coast of China, a series of field campaigns were conducted in 2011, including measurements from a ship cruise, island, and coastal receptor sites. The relationship between BC and CO is presented here for the first ship cruise (C1), the second ship cruise (C2), an island site (Changdao Island, CD), and a coastal site (Wenling, WL). The average BC mass concentrations were 2.43, 2.73, 1.09, 0.94, and 0.77 mu g m(-3) for CD, WL, C1-YS (Yellow Sea), C1-ES (East China Sea), and C2-ES, respectively. For those locations, the average CO mixing ratios were 0.55, 0.48, 0.31, 0.36, and 0.27 ppm. The high loadings of both BC and CO imply severe anthropogenic pollution over the eastern coast of China. Additionally, the linear correlation between BC and CO was regressed for each location. The slopes, i.e., the ratios of Delta BC to Delta CO derived from their relationship, correlated well with the ratios of diesel consumption to gasoline consumption in each province/city, which reveals vehicular emission to be the common source for BC and CO and that there are distinct fuel structures between North and South China. The Delta BC/Delta CO values at coastal sites (Changdao Island and Wenling) were much higher than those over the Yellow Sea and East China Sea, and the correlation coefficients also showed a decreasing trend from the coast to the sea. Therefore, the quantity of Delta BC/Delta CO and the correlation coefficients are possible indicators for the aging and removal of BC.
Methanesulfonic acid (MSA) has been widely used as a proxy for marine biogenic sources, but it is still a challenge to provide an accurate MSA mass concentration with high time resolution. This study offers an improved MSA quantification method using high resolution time of-flight aerosol mass spectrometer (HR-ToF-AMS). Particularly, the method was validated based on an excellent agreement with parallel offline measurements (slope = 0.88, R-2 = 0.89). This comparison is much better than those using previously reported methods, resulting in underestimations of 31-54% of MSA concentration. With this new method, MSA mass concentrations were obtained during 4 North/South Atlantic cruises in spring and autumn of 2011 and 2012. The seasonal and spatial variation of the particulate MSA mass concentration as well as the MSA to non-sea-salt sulfate ratio (MSA:nssSO(4)) over the North/South Atlantic Ocean were determined for the first time. Seasonal variation of the MSA mass concentration was observed, with higher values in spring (0.03 mu g m(-3)) than in autumn (0.01 mu g m(-3)). The investigation of MSA:nssSO(4) suggests a ubiquitous and significant influence of anthropogenic sources on aerosols in the marine boundary layer.
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 15-615 nm, and the median particle number concentrations (PNCs) were found to vary in the range of 0.3 x 10(4)-2.2 x 10(4) cm(-3) at the urban sites and were approximately 0.2 x 10(4) cm(-3) at the background site. The peak diameters at the different sites varied largely from 22 to 102 nm. The PNCs in the Aitken mode (25-100 nm) 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 urbansites and NPF events. The frequencies of NPF events at the different siteswere 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 bemore 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. (C) 2016 The Research Center for Eco-Environmental Sciences, Chinese Academy of Sciences. Published by Elsevier B.V.
Rapid economic development and urbanization in China has been concentrated in coastal cities, resulting in haze and photochemical smog issues, especially in the densely-populated Yangtze River Delta. In this study, we explore particulate matter (specifically PM2.5) pollution in a city in Zhejiang Province (Ningbo), chosen to represent a typical, densely-populated urban city with residential and industrial sections. PM2.5 samples were collected at five sites in four seasons from Dec. 2012 to Nov. 2013. The annual average PM2.5 mass concentration was 53.2 +/- 30.4 mu g/m(3), with the highest concentration in winter and lowest in summer. Among the five sites, PM2.5 concentration was highest in an urban residential site and lowest in a suburban site, due to effects of urbanization and the anthropogenic influences. The chemical components of PM2.5 show significant seasonal variation. In addition, secondary transformation was high in Ningbo, with the highest proportion of secondary components found at a suburban site and the lowest at the industrial sites. Ningbo is controlled by five major air masses originating from inland China, from the Bohai Sea, offshore from the southeast, the Yellow Sea, and off the east coast of Korea. The relative contributions of these air masses differ, by season, with the Bohai Sea air mass dominating in winter and spring, the maritime southeast air mass in summer, and the YellowSea and coastal Korean air masses dominating in autumn. The continental air mass is associated with a high PM2.5 concentration, indicating that it is primarily transports primary emissions. In contrast, the concentration ratios among secondary formed pollutants were higher in the maritime air masses, which suggests that sea breezes control temporal and spatial variations of air pollution over coastal cities. (C) 2017 Published by Elsevier B.V.
This review presents an overview of the analytical techniques for detecting the phase state of secondary organic aerosol (SOA), the effects of phase state on mass transport, and the types of SOA being studied. The previous studies showed that SOA could be solid, semi-solid, or liquid. The bulk diffusion coefficients for solid and semi-solid can be much smaller than those for liquid SOA, and therefore lead to limited mass transfer of species and different formation and transformation of SOA compared to liquid systems. However, only several types of SOA precursors have been studied, such as alpha-pinene, isoprene, and toluene. The phase state of SOA in urban areas as well as the effects of coexisting inorganic species on their phase state is largely unknown. Our analysis shows that the phase state perhaps play an important role in the rapid increase of secondary particle mass concentration during heavily hazed events. Therefore, it is important to study the phase state of SOA and the absorption and transfer of the key active gases at the surface and in the bulk of aerosols in the polluted environments, which will help us to further understand the mechanisms of the formation and evolution of secondary particles in China.总结了国内外对二次有机气溶胶(SOA)相态的研究进展,结果显示不同条件下SOA可能是固态、不定形态、液态.固态和不定形态SOA的体相扩散系数远低 于液态SOA,从而阻碍SOA的物质传输和化学转化等物理化学过程.目前,SOA相态的研究主要集中在有限体系,例如alpha-蒎烯、异戊二烯、甲苯等 挥发性有机物为前体物产生的SOA,缺乏实际大气SOA的相态信息.此外,对无机盐影响SOA相态的认识也十分有限.本文提出重污染形成过程中,相态可能 是二次颗粒物快速增长、转化的重要影响因素之一.因此,结合外场观测、实验室研究以及多层动力学模型研究重污染形成过程中SOA的相态及其对关键反应活性 气体的吸附、传输等影响机制,有助于深入理解我国复合大气污染条件下二次颗粒物的生成转化机制.
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 fin 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)(2)SO4 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.