Xiao-Feng Huang

Source apportionment and secondary organic aerosol estimation of PM 2.5 in an urban atmosphere in China

PM2.5 is the key pollutant in atmospheric pollution in China. With new national air quality standards taking effect, PM2.5 has become a major issue for future pollution control. To effectively prevent and control PM2.5, its emission sources must be precisely and thoroughly understood. However, there are few publications reporting comprehensive and systematic results of PM2.5 source apportionment in the country. Based on PM2.5 sampling during 2009 in Shenzhen and follow-up investigation, positive matrix factorization (PMF) analysis has been carried out to understand the major sources and their temporal and spatial variations. The results show that in urban Shenzhen (University Town site), annual mean PM2.5 concentration was 42.2 μg m−3, with secondary sulfate, vehicular emission, biomass burning and secondary nitrate as major sources; these contributed 30.0%, 26.9%, 9.8% and 9.3% to total PM2.5, respectively. Other sources included high chloride, heavy oil combustion, sea salt, dust and the metallurgical industry, with contributions between 2%–4%. Spatiotemporal variations of various sources show that vehicular emission was mainly a local source, whereas secondary sulfate and biomass burning were mostly regional. Secondary nitrate had both local and regional sources. Identification of secondary organic aerosol (SOA) has always been difficult in aerosol source apportionment. In this study, the PMF model and organic carbon/elemental carbon (OC/EC) ratio method were combined to estimate SOA in PM2.5. The results show that in urban Shenzhen, annual SOA mass concentration was 7.5 μg m−3, accounting for 57% of total organic matter, with precursors emitted from vehicles as the major source. This work can serve as a case study for further in-depth research on PM2.5 pollution and source apportionment in China.

Elemental composition of organic aerosol: The gap between ambient and laboratory measurements

A large data set including surface, aircraft, and laboratory observations of the atomic oxygen-to-carbon (O:C) and hydrogen-to-carbon (H:C) ratios of organic aerosol (OA) is synthesized and corrected using a recently reported method. The whole data set indicates a wide range of OA oxidation and a trajectory in the Van Krevelen diagram, characterized by a slope of −0.6, with variation across campaigns. We show that laboratory OA including both source and aged types explains some of the key differences in OA observed across different environments. However, the laboratory data typically fall below the mean line defined by ambient observations, and little laboratory data extend to the highest O:C ratios commonly observed in remote conditions. OA having both high O:C and high H:C are required to bridge the gaps. Aqueous-phase oxidation may produce such OA, but experiments under realistic ambient conditions are needed to constrain the relative importance of this pathway.

Characterization of submicron aerosols in the urban outflow of the central Pearl River Delta region of China

Submicron aerosol particles (with aerodynamic diameters less than 1 μm, PM1) were sampled and measured in Heshan, an urban outflow site of Guangzhou megacity in Pearl River Delta in South China, using an Aerodyne High-Resolution Time-of-Flight Aerosol Mass Spectrometer (HR-ToF-AMS) in November 2010 during 2010 Guangzhou Asian Games. The mean PM1 mass concentration measured was 47.9 ± 17.0 μg·m−3 during the campaign, with organic aerosol (OA) and sulfate being the two dominant species, accounting for 36.3% and 20.9% of the total mass, respectively, followed by black carbon (17.1%, measured by an aethalometer), nitrate (12.9%), ammonium (9.6%) and chloride (3.1%). The average size distributions of the species (except black carbon) were dominated by an accumulation mode peaking at ∼550 nm. Calculations based on high-resolution organic mass spectrum showed that, C, H, O and N on average contributed 58.1%, 7.3%, 30.7%, and 3.9% to the total organic mass, respectively. The average ratio of organic mass over organic carbon mass (OM/OC) was 1.73 ± 0.08. Four components of OA were identified by the Positive Matrix Factorization (PMF) analysis, including a hydrocarbon-like (HOA), a biomass burning (BBOA) and two oxygenated (SV-OOA and LV-OOA) organic aerosol components, which on average accounted for 18.0%, 14.3%, 28.8% and 38.9% of the total organic mass, respectively.

Gas-to-particle conversion of atmospheric ammonia and sampling artifacts of ammonium in spring of Beijing

PM2.5 and gaseous pollutants (SO2, HNO2, HNO3, HCl, and NH3) were simultaneously collected by Partisol® Model 2300 Sequential Speciation Sampler with denuder-filter pack system in the spring of 2013 in Beijing. Water-soluble inorganic ions and gaseous pollutants were measured by Ion Chromatography. Results showed that the concentrations of NH3, NH4+ and PM2.5 had similar diurnal variation trends and their concentrations were higher at night than in daytime. The results of gas-to-particle conversion revealed that [NH3]:[NH4+] ratio was usually higher than 1; however, it was less than 1 and the concentration of NH4+ increased significantly during the haze episode, indicating that NH3 played an important role in the formation of fine particle. Research on the sampling artifacts suggested that the volatilization loss of NH4+ was prevalent in the traditional single filter-based sampling. The excess loss of HNO3 and HCl resulted from ammonium-poor aerosols and semivolatile inorganic species had severe losses in the clean day, whereas the mass of NH4+ was usually overestimated during the single filter-based sampling due to the positive artifacts. Correlation analysis was used to evaluate the influence of meteorological conditions on the volatilization loss of NH4+. It was found that the average relative humidity and temperature had great effects on the loss of NH4+. The loss of NH4+ was significantly under high temperature and low humidity, and tended to increase with the increasing of absorption of gaseous pollutants by denuder. The total mass of volatile loss of NH4+, NO3− and Cl− could not be ignored and its maximum value was 12.17 μg m−3. Therefore it is important to compensate sampling artifacts for semivolatile inorganic species.

Temporal and spatial distribution of PM2.5 chemical composition in a coastal city of Southeast China

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±30.4μg/m3, 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 Yellow Sea 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.

Molecular Characterization of Nitrogen-Containing Organic Compounds in Humic-like Substances Emitted from Straw Residue Burning

The molecular composition of humic-like 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.

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.

Differentiating local and regional sources of Chinese urban air pollution based on effect of Spring Festival

The emission of pollutants is extremely reduced during the annual Chinese Spring Festival (SF) in Shenzhen, China. During the SF, traffic flow drops by ∼ 50 % and the industrial plants are almost entirely shut down in Shenzhen. To characterize the variation in ambient air pollutants due to the “Spring Festival effect”, various gaseous and particulate pollutants were measured in real time in urban Shenzhen over three consecutive winters (2014–2016). The results indicate that the concentrations of NOx , volatile organic compounds (VOCs), black carbon (BC), primary organic aerosols, chloride, and nitrate in submicron aerosols decrease by 50–80 % during SF periods relative to non-Spring Festival periods, regardless of meteorological conditions. This decrease suggests that these pollutants are mostly emitted or secondarily formed from urban local emissions. The concentration variation in species mostly from regional or natural sources, however, is found to be much less, such as for bulk fine particulate matter (PM2.5). More detailed analysis of the Spring Festival effect reveals an urgent need to reduce emissions of SO2 and VOCs on a regional scale rather than on an urban scale to reduce urban PM2.5 in Shenzhen, which can also be useful as a reference for other megacities in China.

Characteristics and aging of traffic-derived particles in a highway tunnel at a coastal city in southern China

Road traffic is one of the major sources of particulate matters in the atmosphere. Tunnels provide a semi-closed place to measure traffic-derived particles before the particles were photo-chemically modified in the open air. In this study, aerosol particles were collected in a tunnel, and an urban site for comparison at a coastal city in south China. The particles were analyzed by using a transmission electron microscope coupled with an energy-dispersive X-ray spectrometry. There were four groups of particles according to sources: tailpipe-emitted particles, wear debris, road dust, and secondary particles. Tailpipe-emitted particles included soot, organic, and a part of sulfate and metal particles. Wear debris were characterized by their distinct metal components. Road dust was composed of mineral particles and fly ash. Secondary particles were some sulfate particles and mixture particles. Sulfate particles were further divided into two subtypes: with and without organic coating. Sulfate particles with organic coating accounted for 56.2% of total sulfate particles in the tunnel, while the percentage was 36.9% at the urban site, indicating that sulfate particles were more easily coated by organics in the tunnel than the urban site. However, the aging degree of sulfate particles in the tunnel was weaker than that at the urban site, which was attributed to the absence of photochemical reactions in the tunnel environment. Some mixture particles had a core-shell structure (C-S particles). The composition and morphologies of the cores of the C-S particles were similar to those of mineral, metal, and mixture particles. The shells of the C-S particles were mainly composed of organics. The C-S particles were more aged than the sulfate particles with coating in the tunnel environment, suggesting that mineral and metal components could efficiently enhance particle aging in the absence of photochemical reactions.

Volatility measurement of atmospheric submicron aerosols in an urban atmosphere in southern China

Aerosol pollution has been a very serious environmental problem in China for many years. The volatility of aerosols can affect the distribution of compounds in the gas and aerosol phases, the atmospheric fates of the corresponding components 10 and the measurement of the concentration of aerosols. Compared to the characterization of chemical composition, few studies have focused on the volatility of aerosols in China. In this study, a Thermo-Denuder – Aerosol Mass Spectrometer (TD-AMS) system was deployed to study the volatility of non-refractory submicron particulate matter (PM1) species during winter in Shenzhen. To our knowledge, this paper is the first report of the volatilities of aerosol chemical components based on a TDAMS system in China. The average PM1 mass concentration during the experiment was 42.7 ± 20.1 μg m, with organic 15 aerosol (OA) being the most abundant component (43.2% of the total mass). The volatility of chemical species measured by the AMS varied, with nitrate showing the highest volatility, with a mass fraction remaining (MFR) of 0.57 at 50 °C. Organics showed semi-volatile characteristics (the MFR was 0.88 at 50 °C), and the volatility had a relatively linear correlation with the TD temperature (from the ambient temperature to 200 °C), with an evaporation rate of 0.45 %·°C. Five subtypes of OA were resolved from total OAs by positive matrix factorization (PMF) for data obtained under both ambient temperature and high 20 temperatures through the TD, including a hydrocarbon-like OA (HOA, accounting for 13.5%), a cooking OA (COA, 20.6%), a biomass burning OA (BBOA, 8.9%) and two oxygenated OAs (OOA): a less-oxidized OOA (LO-OOA, 39.1%) and a moreoxidized OOA (MO-OOA, 17.9%). Different OA factors presented different volatilities, and the volatility sequence of the OA factors at 50 °C was HOA (MFR of 0.56) > LO-OOA (0.70) > COA (0.85) ≈ BBOA (0.87)> MO-OOA (0.99), which was not completely consistent with the sequence of their O/C ratios. The high volatility of HOA implied that it had a high potential to 25 be oxidized to secondary species in the gas phase. The aerosol volatility measurement results in this study provide useful parameters for the modelling work of aerosol evolution in China and are also helpful in understanding the formation mechanisms of secondary aerosols.