Aromatic hydrocarbons as ozone precursors before and after outbreak of the 2008 financial crisis in the Pearl River Delta region, south China

In the second half of 2008 China's highly industrialized Pearl River Delta (PRD) region was hard-hit by the financial crisis (FC). This study reports volatile organic compounds measured in the PRD during November-December in both 2007 before the FC and 2008 after the FC. While total mixing ratios of non-methane hydrocarbons (NMHCs) on average were only about 7% lower from 40.2 ppbv in 2007 to 37.5 ppbv in 2008, their ozone formation potentials (OFPs) dropped about 30%, resulting from about 55% plummet of aromatic hydrocarbons (AHs) against a greater than 20% increase of total alkanes/alkenes. The elevated alkanes and alkenes in 2008 could be explained by greater emissions from vehicle exhausts and LPG combustion due to rapid increase of vehicle numbers and LPG consumption; the drop of AHs could be explained by reduced emissions from industries using AH-containing solvents due to the influence of the FC, as indicated by much lower ratios of toluene to benzene and of xylenes/ trichloroethylene/tetrachloroethylene to carbon monoxide (CO) in 2008. Source apportionment by positive matrix factorization (PMF) also revealed much less contribution of industry solvents to total anthropogenic NMHCs and particularly to toluene and xylenes in 2008 than in 2007. Based on PMF reconstructed source contributions, calculated OFPs by industrial emissions were responsible for 40.8% in 2007 in contrast to 18.4% in 2008. Further investigation into local industry output statistics suggested that the plummet of AHs in 2008 should be attributed to small enterprises, which contributed largely to ambient AHs due to their huge numbers and non-existent emission treatment, but were much more influenced by the FC. © 2012. American Geophysical Union. All Rights Reserved

Acetone in the Atmosphere of Hong Kong, Abundance, Sources and Photochemical Precursors

Intensive field measurements were carried out at a mountain site and an urban site at the foot of the mountain from September to November 2010 in Hong Kong. Acetone was monitored using both canister air samples and 2,4-dinitrophenylhydrazine cartridges. The spatiotemporal patterns of acetone showed no difference between the two sites (p > 0.05), and the mean acetone mixing ratios on O3 episode days were higher than those on non-O3 episode days at both sites (p < 0.05). The source contributions to ambient acetone at both sites were estimated using a receptor model i.e. Positive Matrix Factorization (PMF). The PMF results showed that vehicular emission and secondary formation made the most important contribution to ambient acetone, followed by the solvent use at both sites. However, the contribution of biogenic emission at the mountain site was significantly higher than that at the urban site, whereas biomass burning made more remarkable contribution at the urban site than that at the mountain site. The mechanism of oxidation formation of acetone was investigated using a photochemical box model. The results indicated that i-butene was the main precursor of secondary acetone at the mountain site, while the oxidation of i-butane was the major source of secondary acetone at the urban site.Department of Civil and Environmental Engineerin

Ozone production in four major cities of China: sensitivity to ozone precursors and heterogeneous processes

Abstract. Despite a large volume of research over a number of years, our understandings of the key precursors that control tropospheric ozone production and the impacts of heterogeneous processes remain incomplete. In this study, we analyze measurements of ozone and its precursors made at rural/suburban sites downwind of four large Chinese cities – Beijing, Shanghai, Guangzhou and Lanzhou. At each site the same measurement techniques were utilized and a photochemical box model based on the Master Chemical Mechanism (v3.2) was applied, to minimize uncertainties in comparison of the results due to differences in methodology. All four cities suffered from severe ozone pollution. At the rural site of Beijing, export of the well-processed urban plumes contributed to the extremely high ozone levels (up to an hourly value of 286 ppbv), while the pollution observed at the suburban sites of Shanghai, Guangzhou and Lanzhou was characterized by intense in-situ ozone production. The major anthropogenic hydrocarbons were alkenes and aromatics in Beijing and Shanghai, aromatics in Guangzhou, and alkenes in Lanzhou. The ozone production was found to be in a VOCs-limited regime in both Shanghai and Guangzhou, and a mixed regime in Lanzhou. In Shanghai, the ozone formation was most sensitive to aromatics and alkenes, while in Guangzhou aromatics were the predominant ozone precursors. In Lanzhou, either controlling NOx or reducing emissions of olefins from the petrochemical industry would mitigate the local ozone production. The potential impacts of several heterogeneous processes on the ozone formation were assessed. The hydrolysis of dinitrogen pentoxide (N2O5), uptake of the hydroperoxyl radical (HO2) on particles, and surface reactions of NO2 forming nitrous acid (HONO) present considerable sources of uncertainty in the current studies of ozone chemistry. Further efforts are urgently required to better understand these processes and refine atmospheric models

Seasonal and Diurnal Variations of Atmospheric Non-Methane Hydrocarbons in Guangzhou, China

In recent decades, high ambient ozone concentrations have become one of the major regional air quality issues in the Pearl River Delta (PRD) region. Non-methane hydrocarbons (NMHCs), as key precursors of ozone, were found to be the limiting factor in photochemical ozone formation for large areas in the PRD. For source apportioning of NMHCs as well as ozone pollution control strategies, it is necessary to obtain typical seasonal and diurnal patterns of NMHCs with a large pool of field data. To date, few studies have focused on seasonal and diurnal variations of NMHCs in urban areas of Guangzhou. This study explored the seasonal variations of most hydrocarbons concentrations with autumn maximum and spring minimum in Guangzhou. The diurnal variations of most anthropogenic NMHCs typically showed two-peak pattern with one at 8:00 in the morning and another at 20:00 in the evening, both corresponding to traffic rush hours in Guangzhou, whereas isoprene displayed a different bimodal diurnal curve. Propene, ethene, m, p-xylene and toluene were the four largest contributors to ozone formation in Guangzhou, based on the evaluation of individual NMHCs’ photochemical reactivity. Therefore, an effective strategy for controlling ozone pollution may be achieved by the reduction of vehicle emissions in Guangzhou

Effect of isoprene emissions from major forests on ozone formation in the city of Shanghai, China

Ambient surface level concentrations of isoprene (C<sub>5</sub>H<sub>8</sub>) were measured in the major forest regions located south of Shanghai, China. Because there is a large coverage of broad-leaved trees in this region, high concentrations of isoprene were measured, ranging from 1 to 6 ppbv. A regional dynamical/chemical model (WRF-Chem) is applied for studying the effect of such high concentrations of isoprene on the ozone production in the city of Shanghai. The evaluation of the model shows that the calculated isoprene concentrations agree with the measured concentrations when the measured isoprene concentrations are lower than 3 ppb, but underestimate the measurements when the measured values are higher than 3 ppb. Isoprene was underestimated only at sampling sites near large bamboo plantations, a high isoprene source, indicating the need to include geospatially resolved bamboo distributions in the biogenic emission model. The assessment of the impact of isoprene on ozone formation suggests that the concentrations of peroxy radicals (RO<sub>2</sub>) are significantly enhanced due to the oxidation of isoprene, with a maximum of 30 ppt. However, the enhancement of RO<sub>2</sub> is confined to the forested regions. Because the concentrations of NO<sub>x</sub> were low in the forest regions, the ozone production due to the oxidation of isoprene (C<sub>5</sub>H<sub>8</sub> + OH → → RO<sub>2</sub> + NO → → O<sub>3</sub>) is low (less than 2–3 ppb h<sup>−1</sup>). The calculation further suggests that the oxidation of isoprene leads to the enhancement of carbonyls (such as formaldehyde and acetaldehyde) in the regions downwind of the forests, due to continuous oxidation of isoprene in the forest air. As a result, the concentrations of HO<sub>2</sub> radical are enhanced, resulting from the photo-disassociation of formaldehyde and acetaldehyde. Because the enhancement of HO<sub>2</sub> radical occurs in regions downwind of the forests, the enhancement of ozone production (6–8 ppb h<sup>−1</sup>) is higher than in the forest region, causing by higher anthropogenic emissions of NO<sub>x</sub>. This study suggests that the biogenic emissions in the major forests to the south of Shanghai have important impacts on the levels of ozone in the city, mainly due to the carbonyls produced by the continuous oxidation of isoprene in the forest air