Liping Qiao

A case study of the highly time-resolved evolution of aerosol chemical and optical properties in urban Shanghai, China

Characteristics of the chemical and optical properties of aerosols in urban Shanghai and their relationship were studied over a three-day period in October 2011. A suite of real-time instruments, including an Aerosol Time-Of-Flight Mass Spectrometer (ATOFMS), a Monitor for AeRosols and GAses (MARGA), a Cavity Ring Down Spectrometer (CRDS), a nephelometer and a Scanning Mobility Particle Sizer (SMPS), was employed to follow the quick changes of the aerosol properties within the 72 h sampling period. The origin of the air mass arriving in Shanghai during this period shifted from the East China Sea to the northwest area of China, offering a unique opportunity to observe the evolution of aerosols influenced by regional transport from the most polluted areas in China. According to the meteorological conditions and temporal characterizations of the chemical and optical properties, the sampling period was divided into three periods. During Period 1 (00:00–23:00 LT, 13 October), the aerosols in urban Shanghai were mainly fresh and the single scattering albedo varied negatively with the emission of elemental carbon, indicating that local sources dominated. Period 2 (23:00 LT on 13 October to 10:00 LT on 15 October) was impacted by regionally transported pollutants and had the highest particulate matter (PM) mass loading and the lowest particle acidity, characterized by large fractions of aged particles and high secondary ion (nitrate, sulfate and ammonium) mass concentrations. Comparison between ATOFMS particle acidity and quantitative particle acidity by MARGA indicated the significance of semi-quantitative calculation in ATOFMS. Two sub-periods were identified in Period 2 based on the scattering efficiency of PM 1 mass. Period 3 (from 10:00 LT on 15 October to 00:00 LT on 16 October) had a low PM1/PM10 ratio and a new particle formation event. The comparison of these sub-periods highlights the influence of particle mixing state on aerosol optical properties. We directly observed the influence of regionally transported pollutants on local aerosol properties and demonstrate that the PM mass extinction efficiency is largely determined by the mixing states of the aerosol.

Chemical and optical properties of aerosols and their interrelationship in winter in the megacity Shanghai of China

A field campaign on air quality was carried out in Shanghai in winter of 2012. The concentrations of NO, NO2, NOx, SO2, CO, and PM2.5 increased during haze formation. The average masses of SO4(2-), NO3(-) and NH4(+) were 10.3, 11.7 and 6.7 μg/m(3) during the haze episodes, which exceeded the average (9.2, 7.9, and 3.4 μg/m(3)) of these components in the non-haze days. The mean values for the aerosol scattering coefficient (bsp), aerosol absorption coefficient (bap) and single scattering albedo (SSA) were 288.7, 27.7 and 0.91 Mm(-1), respectively. A bi-peak distribution was observed for the mass concentrations of CO, NO, NO2, and NOx. More sulfate was produced during daytime than that in the evening due to photochemical reactions. The mass concentration of NH4(+) achieved a small peak at noontime. NO3(-) showed lower concentrations in the afternoon and higher concentrations in the early morning. There were obvious bi-peak diurnal patterns for bsp and bap as well as SSA. bsp and bap showed a positive correlation with PM2.5 mass concentration. (NH4)2SO4, NH4NO3, organic mass, elemental carbon and coarse mass accounted for 21.7%, 19.3%, 31.0%, 9.3% and 12.3% of the total extinction coefficient during non-haze days, and 25.6%, 24.3%, 30.1%, 8.1% and 8.2% during hazy days. Organic matter was the largest contributor to light extinction. The contribution proportions of ammonium sulfate and ammonium nitrate to light extinction were significantly higher during the hazy time than during the non-haze days.

Chemical characteristics of fine particles and their impact on visibility impairment in Shanghai based on a 1-year period observation.

In this work, a one-year observation focusing on high time resolution characteristics of components in fine particles was conducted at an urban site in Shanghai. Contributions of different components on visibility impairment were also studied. Our research indicates that the major components of PM2.5 in Shanghai are water-soluble inorganic ions and carbonaceous aerosol, accounting for about 60% and 30% respectively. Higher concentrations of sulfate (SO42-) and organic carbon (OC) in PM2.5 occurred in fall and summer, while higher concentrations of nitrate (NO3-) were observed in winter and spring. The mass concentrations of Cl- and K+ were higher in winter. Moreover, NO3- increased significantly during PM2.5 pollution episodes. The high values observed for the sulfate oxidizing rate (SOR), nitrate oxidizing rate (NOR) and secondary organic carbon (SOC) in OC indicate that photochemical reactions were quite active in Shanghai. The IMPROVE (Interagency Monitoring of Protected Visual Environments) formula was used in this study to investigate the contributions of individual PM2.5 chemical components to the light extinction efficient in Shanghai. Both NH4NO3 and (NH4)2SO4 had close relationships with visibility impairment in Shanghai. Our results show that the reduction of anthropogenic SO2, NOx and NH3 would have a significant effect on the improvement of air quality and visibility in Shanghai.

Potential particulate pollution derived from UV-induced degradation of odorous dimethyl sulfide

UV-induced degradation of odorous dimethyl sulfide (DMS) was carried out in a static White cell chamber with UV irradiation. The combination of in situ Fourier transform infrared (FT-IR) spectrometer, gas chromatograph-mass spectrometer (GC-MS), wide-range particle spectrometer (WPS) technique, filter sampling and ion chromatographic (IC) analysis was used to monitor the gaseous and potential particulate products. During 240 min of UV irradiation, the degradation efficiency of DMS attained 20.9%, and partially oxidized sulfur-containing gaseous products, such as sulfur dioxide (SO2), carbonyl sulfide (OCS), dimethyl sulfoxide (DMSO), dimethyl sulfone (DMSO2) and dimethyl disulfide (DMDS) were identified by in situ FT-IR and GC-MS analysis, respectively. Accompanying with the oxidation of DMS, suspended particles were directly detected to be formed by WPS techniques. These particles were measured mainly in the size range of accumulation mode, and increased their count median diameter throughout the whole removal process. IC analysis of the filter samples revealed that methanesulfonic acid (MSA), sulfuric acid (H2SO4) and other unidentified chemicals accounted for the major non-refractory compositions of these particles. Based on products analysis and possible intermediates formed, the degradation pathways of DMS were proposed as the combination of the O(1D)- and the OH- initiated oxidation mechanisms. A plausible formation mechanism of the suspended particles was also analyzed. It is concluded that UV-induced degradation of odorous DMS is potentially a source of particulate pollutants in the atmosphere.

Do vehicular emissions dominate the source of C6–C8 aromatics in the megacity Shanghai of eastern China?

The characteristic ratios of volatile organic compounds (VOCs) to i-pentane, the indicator of vehicular emissions, were employed to apportion the vehicular and non-vehicular contributions to reactive species in urban Shanghai. Two kinds of tunnel experiments, one tunnel with more than 90% light duty gasoline vehicles and the other with more than 60% light duty diesel vehicles, were carried out to study the characteristic ratios of vehicle-related emissions from December 2009 to January 2010. Based on the experiments, the characteristic ratios of C6-C8 aromatics to i-pentane of vehicular emissions were 0.53 ± 0.08 (benzene), 0.70 ± 0.12 (toluene), 0.41 ± 0.09 (m,p-xylenes), 0.16 ± 0.04 (o-xylene), 0.023 ± 0.011 (styrene), and 0.15 ± 0.02 (ethylbenzene), respectively. The source apportionment results showed that around 23.3% of C6-C8 aromatics in urban Shanghai were from vehicular emissions, which meant that the non-vehicular emissions had more importance. These findings suggested that emission control of non-vehicular sources, i.e. industrial emissions, should also receive attention in addition to the control of vehicle-related emissions in Shanghai. The chemical removal of VOCs during the transport from emissions to the receptor site had a large impact on the apportionment results. Generally, the overestimation of vehicular contributions would occur when the VOC reaction rate constant with OH radicals (kOH) was larger than that of the vehicular indicator, while for species with smaller kOH than the vehicular indicator, the vehicular contribution would be underestimated by the method of characteristic ratios.

Insights into extinction evolution during extreme low visibility events: Case study of Shanghai, China

Apportionment of ambient extinction coefficient is essential for quantifying the causes of visibility degradation. Previous studies focused on either seasonal or episode-average extinction coefficients. The extinction evolution during different types of low visibility events was still unclear and seldom investigated. In this study, hourly-resolution apportionment of ambient extinction coefficient, including dry extinction coefficient and hygroscopic portion, during three low visibility events (i.e., dust storm, autumn and winter haze) and one clear episode was retrieved through online measurement in Shanghai, China. PM2.5 soil and coarse particles contributed 90% of PM10 mass and 62% of total extinction coefficient throughout the dust storm event. Secondary inorganic aerosol and organic matter dominated the autumn and winter haze events, accounting for 52% and 31% of PM2.5 mass, 35% and 27% of extinction coefficient, respectively. Hygroscopic enhancement by inorganic particles contributed another 22-27% of extinction coefficient during the two haze events. However, higher relative humidity elevated the extinction percentage of inorganic aerosol and hygroscopic enhancement during the autumn haze, and the percentage of organic matter decreased correspondingly. In contrast, the extinction of each contributor increased proportionally and the percentages could keep at a stable level during the winter haze. Furthermore, the mass extinction efficiency of major PM2.5 chemical components was found to increase with the accumulation of mass loading. These findings indicated the importance of reducing the mass level of organic matter and secondary inorganic aerosol during the autumn or winter haze events. The control of precursors of sulfur and nitrogen oxides seemed more effective for visibility improvement during the autumn events with higher relative humidity.

Atmospheric new particle formation from sulfuric acid and amines in a Chinese megacity

A puzzle of new particles Atmospheric particulates can be produced by emissions or form de novo. New particle formation usually occurs in relatively clean air. This is because preexisting particles in the atmosphere will scavenge the precursors of new particles and suppress their formation. However, observations in some heavily polluted megacities have revealed substantial rates of new particle formation despite the heavy loads of ambient aerosols. Yao et al. investigated new particle formation in Shanghai and describe the conditions that make this process possible. The findings will help inform policy decisions about how to reduce air pollution in these types of environments. Science, this issue p. 278 Atmospheric new particle formation in heavily polluted cities can occur in certain chemical environments. Atmospheric new particle formation (NPF) is an important global phenomenon that is nevertheless sensitive to ambient conditions. According to both observation and theoretical arguments, NPF usually requires a relatively high sulfuric acid (H2SO4) concentration to promote the formation of new particles and a low preexisting aerosol loading to minimize the sink of new particles. We investigated NPF in Shanghai and were able to observe both precursor vapors (H2SO4) and initial clusters at a molecular level in a megacity. High NPF rates were observed to coincide with several familiar markers suggestive of H2SO4–dimethylamine (DMA)–water (H2O) nucleation, including sulfuric acid dimers and H2SO4-DMA clusters. In a cluster kinetics simulation, the observed concentration of sulfuric acid was high enough to explain the particle growth to ~3 nanometers under the very high condensation sink, whereas the subsequent higher growth rate beyond this size is believed to result from the added contribution of condensing organic species. These findings will help in understanding urban NPF and its air quality and climate effects, as well as in formulating policies to mitigate secondary particle formation in China.

Emission factors of particulate and gaseous compounds from a large cargo vessel operated under real-world conditions

On-board emissions measurements were performed on a Handysize-class bulk carrier operating under real-world conditions. Emission factors (EFs) were determined for criteria pollutants such as NOx, CO, total hydrocarbons (THC), and PM; PM composition, including organic and elemental carbon (OC and EC), inorganic species, and a variety of organic compounds and VOC species (including alkanes, alkenes, single-ring aromatics, and oxygenated VOCs) were also analyzed. To investigate the impacts of engine type, fuel, and operating conditions on emissions, measurements were conducted on one main and one auxiliary engines using low- and high-sulfur fuels (LSF and HSF) under actual operating conditions, including at-berth, maneuvering, and cruising at different engine loads. OC was the most abundant PM component (contributing 45-65%), followed by sulfate (2-15%) and EC (1-20%). Compounds with 3 or 4 aromatic rings, including phenanthrene, fluoranthene, pyrene, and benzo[b+k]fluoranthene, dominated the particulate polycyclic aromatic hydrocarbons (PAHs) emitted from the ship, accounting for 69-89% of the total PAHs. Single-ring aromatics constituted 50-78% of the emitted VOCs and were dominated by toluene. In this study, switching from HSF (1.12% S) to LSF (0.38% S) reduced emitted PM by 12%, OC by 20%, sulfate by 71%, and particulate PAHs by 94%, but caused an increase in single-ring aromatics. The power-based EFs generally decreased with increasing engine loads. However, decreasing the ship engine load also reduced the vessel speed and, thus, decreased emissions over a given voyage distance. Herein, a Vessel Speed Reduction (VSR) from 11 to 8-9 knots decreased NOx and PM emissions by approximately 33% and 36%, respectively, and OC, EC, sulfate, and particulate PAHs in PM emissions by 34%, 83%, 29%, and 11%. These data can be used to minimize uncertainty in the emission factors used in ship emissions calculations.