Source profiles and reactivity of volatile organic compounds from anthropogenic sources of a megacity in southwest China

Author(s):  
Zihang Zhou ◽  
Qinwen Tan ◽  
Ye Deng ◽  
Chengwei Lu ◽  
Danlin Song ◽  
...  
2018 ◽  
Vol 18 (23) ◽  
pp. 17637-17654 ◽  
Author(s):  
Quanyang Lu ◽  
Yunliang Zhao ◽  
Allen L. Robinson

Abstract. Emissions from mobile sources are important contributors to both primary and secondary organic aerosols (POA and SOA) in urban environments. We compiled recently published data to create comprehensive model-ready organic emission profiles for on- and off-road gasoline, gas-turbine, and diesel engines. The profiles span the entire volatility range, including volatile organic compounds (VOCs, effective saturation concentration C*=107–1011 µg m−3), intermediate-volatile organic compounds (IVOCs, C*=103–106 µg m−3), semi-volatile organic compounds (SVOCs, C*=1–102 µg m−3), low-volatile organic compounds (LVOCs, C*≤0.1 µg m−3) and non-volatile organic compounds (NVOCs). Although our profiles are comprehensive, this paper focuses on the IVOC and SVOC fractions to improve predictions of SOA formation. Organic emissions from all three source categories feature tri-modal volatility distributions (“by-product” mode, “fuel” mode, and “lubricant oil” mode). Despite wide variations in emission factors for total organics, the mass fractions of IVOCs and SVOCs are relatively consistent across sources using the same fuel type, for example, contributing 4.5 % (2.4 %–9.6 % as 10th to 90th percentiles) and 1.1 % (0.4 %–3.6 %) for a diverse fleet of light duty gasoline vehicles tested over the cold-start unified cycle, respectively. This consistency indicates that a limited number of profiles are needed to construct emissions inventories. We define five distinct profiles: (i) cold-start and off-road gasoline, (ii) hot-operation gasoline, (iii) gas-turbine, (iv) traditional diesel and (v) diesel-particulate-filter equipped diesel. These profiles are designed to be directly implemented into chemical transport models and inventories. We compare emissions to unburned fuel; gasoline and gas-turbine emissions are enriched in IVOCs relative to unburned fuel. The new profiles predict that IVOCs and SVOC vapour will contribute significantly to SOA production. We compare our new profiles to traditional source profiles and various scaling approaches used previously to estimate IVOC emissions. These comparisons reveal large errors in these different approaches, ranging from failure to account for IVOC emissions (traditional source profiles) to assuming source-invariant scaling ratios (most IVOC scaling approaches).


2017 ◽  
Vol 607-608 ◽  
pp. 253-261 ◽  
Author(s):  
Wang Hong-li ◽  
Jing Sheng-ao ◽  
Lou Sheng-rong ◽  
Hu Qing-yao ◽  
Li Li ◽  
...  

2017 ◽  
Vol 17 (12) ◽  
pp. 7733-7756 ◽  
Author(s):  
Yu Zhao ◽  
Pan Mao ◽  
Yaduan Zhou ◽  
Yang Yang ◽  
Jie Zhang ◽  
...  

Abstract. Non-methane volatile organic compounds (NMVOCs) are the key precursors of ozone (O3) and secondary organic aerosol (SOA) formation. Accurate estimation of their emissions plays a crucial role in air quality simulation and policy making. We developed a high-resolution anthropogenic NMVOC emission inventory for Jiangsu in eastern China from 2005 to 2014, based on detailed information of individual local sources and field measurements of source profiles of the chemical industry. A total of 56 NMVOCs samples were collected in nine chemical plants and were then analyzed with a gas chromatography – mass spectrometry system (GC-MS). Source profiles of stack emissions from synthetic rubber, acetate fiber, polyether, vinyl acetate and ethylene production, and those of fugitive emissions from ethylene, butanol and octanol, propylene epoxide, polyethylene and glycol production were obtained. Various manufacturing technologies and raw materials led to discrepancies in source profiles between our domestic field tests and foreign results for synthetic rubber and ethylene production. The provincial NMVOC emissions were calculated to increase from 1774 Gg in 2005 to 2507 Gg in 2014, and relatively large emission densities were found in cities along the Yangtze River with developed economies and industries. The estimates were larger than those from most other available inventories, due mainly to the complete inclusion of emission sources and to the elevated activity levels from plant-by-plant investigation in this work. Industrial processes and solvent use were the largest contributing sectors, and their emissions were estimated to increase, respectively, from 461 to 958 and from 38 to 966 Gg. Alkanes, aromatics and oxygenated VOCs (OVOCs) were the most important species, accounting for 25.9–29.9, 20.8–23.2 and 18.2–21.0 % to annual total emissions, respectively. Quantified with a Monte Carlo simulation, the uncertainties of annual NMVOC emissions vary slightly through the years, and the result for 2014 was −41 to +93 %, expressed as 95 % confidence intervals (CI). Reduced uncertainty was achieved compared to previous national and regional inventories, attributed partly to the detailed classification of emission sources and to the use of information at plant level in this work. Discrepancies in emission estimation were explored for the chemical and refinery sectors with various data sources and methods. Compared with the Multi-resolution Emission Inventory for China (MEIC), the spatial distribution of emissions in this work were more influenced by the locations of large point sources, and smaller emissions were found in urban area for developed cities in southern Jiangsu. In addition, discrepancies were found between this work and MEIC in the speciation of NMVOC emissions under the atmospheric chemistry mechanisms CB05 and SAPRC99. The difference in species OLE1 resulted mainly from the updated source profile of building paint use and the differences in other species from the varied sector contributions to emissions in the two inventories. The Community Multi-scale Air Quality (CMAQ) model simulation was applied to evaluate the two inventories, and better performance (indicated by daily 1 h maximum O3 concentrations in Nanjing) were found for January, April and October 2012 when the provincial inventory was used.


2008 ◽  
Vol 8 (1) ◽  
pp. 245-284 ◽  
Author(s):  
B. Langford ◽  
B. Davison ◽  
E. Nemitz ◽  
C. N. Hewitt

Abstract. Concentrations and fluxes of six volatile organic compounds (VOC) were measured above the city of Manchester (UK) during the summer of 2006. A proton transfer reaction-mass spectrometer was used for the measurement of concentrations, and fluxes were calculated using both the disjunct and the virtual disjunct eddy covariance techniques. The two flux systems, which operated in alternate half hours, showed reasonable agreement, with R2 values ranging between 0.2 and 0.8 for the individual analytes. On average, fluxes measured in the disjunct mode were lower than those measured in the virtual mode by approximately 19%, of which at least 8% can be attributed to the differing measurement frequencies of the two systems and the subsequent attenuation of high frequency flux contributions. Observed fluxes are thought to be largely controlled by anthropogenic sources, with vehicle emissions the major contributor. However both evaporative and biogenic emissions may account for a fraction of the isoprene present. Fluxes of the oxygenated compounds were highest on average, ranging between 60–89 μg m−2 h−1, whereas the fluxes of aromatic compounds were lower, between 19–42 μg m−2 h−1. The observed fluxes of benzene were up-scaled to give a city wide emission estimate which was found to be significantly lower than that of the National Atmospheric Emissions Inventory (NAEI).


2014 ◽  
Vol 14 (3) ◽  
pp. 818-828 ◽  
Author(s):  
Hongli Wang ◽  
Shengrong Lou ◽  
Cheng Huang ◽  
Liping Qiao ◽  
Xibin Tang ◽  
...  

2020 ◽  
Author(s):  
Cécile Debevec ◽  
Stéphane Sauvage ◽  
Valérie Gros ◽  
Thérèse Salameh ◽  
Jean Sciare ◽  
...  

Abstract. An original time series of about 300 atmospheric measurements of a wide range of volatile organic compounds (VOCs) has been obtained at a remote Mediterranean station on the northern tip of Corsica Island (Ersa, France) over 25 months from June 2012 to June 2014. This study presents the seasonal variabilities of 25 selected VOCs, and their various associated sources. The VOC speciation was largely dominated by oxygenated VOCs (OVOCs) along with primary anthropogenic VOCs having a long lifetime in the atmosphere. VOC temporal variations are then examined. Primarily of local origin, biogenic VOCs exhibited notable seasonal and interannual variations, related to temperature and solar radiation ones. Anthropogenic compounds have shown an increasing concentration trend in winter (JFM months) followed by a decrease in spring/summer (AMJ/JAS months), and different concentration levels in winter periods of 2013 and 2014. OVOC concentrations were generally higher in summertime, mainly due to secondary and biogenic sources, whereas their concentrations during fall and winter were potentially more influenced by anthropogenic primary/secondary sources. Moreover, an apportionment factorial analysis was applied to a database comprising a selection of 14 primary individual or grouped VOCs by means of the positive matrix factorization (PMF) technique. A PMF solution composed of 5 factors was taken on. It includes a biogenic factor (which contributed 4 % to the total VOC mass), three anthropogenic factors (namely short-lived anthropogenic sources, evaporative sources, and long-lived combustion sources; which together accounted for 57 %), originating from either nearby or more distant emission areas (such as Italy and south of France); and a remaining one (39 %) connected to the regional background pollution. Variations in these main sources impacting VOC concentrations observed at the receptor site are also investigated at seasonal and interannual scales. In spring and summer, VOC concentrations observed at Ersa were the lowest in the 2-yr period, despite higher biogenic source contributions and since anthropogenic sources advected to Ersa were largely influenced by chemical transformations and vertical dispersion phenomena and were mainly of regional origins. During fall and winter, anthropogenic sources showed higher accumulated contributions when European air masses were advected to Ersa and could be associated to potential emission areas located in Italy and possibly more distant ones in central Europe. Higher VOC concentrations during winter 2013 compared to winter 2014 ones could be related to anthropogenic source contribution variations probably governed by emission strength of the main anthropogenic sources identified in this study together with external parameters, i.e. weaker dispersion phenomena and pollutant depletion. High frequency observations collected during several intensive field campaigns conducted at Ersa during the three summers 2012–2014 confirmed findings from bi-weekly samples in terms of summer concentration levels and source apportionment. However, they suggest that higher sampling frequency and temporal resolution, in particular to observe VOC concentrations variation during the daily cycle, are needed to confirm the deconvolution of the different anthropogenic sources identified by PMF approach. Finally, comparisons of the 25 months of observations at Ersa with VOC measurements conducted at 17 other European monitoring stations highlight the representativeness of the Ersa background station for monitoring seasonal variations in VOC regional pollution impacting continental Europe. Nevertheless, winter VOC concentration levels can significantly vary between sites, pointing out spatial variations in anthropogenic source contributions. As a result, Ersa concentration variations in winter were more representative of VOC regional pollution impacting central Europe. Interannual and spatial VOC concentration variations in winter were also significantly impacted by synoptic phenomena influencing meteorological conditions observed in continental Europe, suggesting that short observation periods may reflect the variability of the identified parameters under the specific meteorological conditions of the studied period.


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