C1-C8 volatile organic compounds in the atmosphere of Hong Kong: Overview of atmospheric processing and source apportionment

We present measurements of C1-C8 volatile organic compounds (VOCs) at four sites ranging from urban to rural areas in Hong Kong from September 2002 to August 2003. A total of 248 ambient VOC samples were collected. As expected, the urban and sub-urban sites generally gave relatively high VOC levels. In contrast, the average VOC levels were the lowest in the rural area. In general, higher mixing ratios were observed during winter/spring and lower levels during summer/fall because of seasonal variations of meteorological conditions. A variation of the air mass composition from urban to rural sites was observed. High ratios of ethyne/CO (5.6 pptv/ppbv) and propane/ethane (0.50 pptv/pptv) at the rural site suggested that the air masses over the territory were relatively fresh as compared to other remote regions. The principal component analysis (PCA) with absolute principal component scores (APCS) technique was applied to the VOC data in order to identify and quantify pollution sources at different sites. These results indicated that vehicular emissions made a significant contribution to ambient non-methane VOCs (NMVOCs) levels in urban areas (65±36%) and in sub-urban areas (50±28% and 53±41%). Other sources such as petrol evaporation, industrial emissions and solvent usage also played important roles in the VOC emissions. At the rural site, almost half of the measured total NMVOCs were due to combustion sources (vehicular and/or biomass/biofuel burning). Petrol evaporation, solvent usage, industrial and biogenic emissions also contributed to the atmospheric NMVOCs. The source apportionment results revealed a strong impact of anthropogenic VOCs to the atmosphere of Hong Kong in both urban/sub-urban and rural areas. © 2006 Elsevier Ltd. All rights reserved

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Department of Civil and Environmental Engineerin

Carbonyl sulfide, dimethyl sulfide and carbon disulfide in the Pearl River Delta of southern China: Impact of anthropogenic and biogenic sources

Reduced sulfur compounds (RSCs) such as carbonyl sulfide (OCS), dimethyl sulfide (DMS) and carbon disulfide (CS2) impact radiative forcing, ozone depletion, and acid rain. Although Asia is a large source of these compounds, until now a long-term study of their emission patterns has not been carried out. Here we analyze 16 months of RSC data measured at a polluted rural/coastal site in the greater Pearl River Delta (PRD) of southern China. A total of 188 canister air samples were collected from August 2001 to December 2002. The OCS and CS2 mixing ratios within these samples were higher in autumn/winter and lower in summer due to the influence of Asian monsoon circulations. Comparatively low DMS values observed in this coastal region suggest a relatively low biological productivity during summer months. The springtime OCS levels in the study region (574 ± 40 pptv) were 25% higher than those on other East Asia coasts such Japan, whereas the springtime CS2 and DMS mixing ratios in the PRD (47 ± 38 pptv and 22 ± 5 pptv, respectively) were 3-30 times lower than elevated values that have been measured elsewhere in East Asia (Japan and Korea) at this time of year. Poor correlations were found among the three RSCs in the whole group of 188 samples, suggesting their complex and variable sources in the region. By means of backward Lagrangian particle release simulations, air samples originating from the inner PRD, urban Hong Kong and South China Sea were identified. The mean mixing ratio of OCS in the inner PRD was significantly higher than that in Hong Kong urban air and South China Sea marine air (p < 0.001), whereas no statistical differences were found for DMS and CS2 among the three regions (p > 0.05). Using a linear regression method based on correlations with the urban tracer CO, the estimated OCS emission in inner PRD (49.6 ± 4.7 Gg yr-1) was much higher than that in Hong Kong (0.32 ± 0.05 Gg yr-1), whereas the estimated CS2 and DMS emissions in the study region accounted for a very few percentage of the total CS2 and DMS emission in China. These findings lay the foundation for better understanding sulfur chemistry in the greater PRD region of southern China. © 2010 Elsevier Ltd

Source origins, modeled profiles, and apportionments of halogenated hydrocarbons in the greater Pearl River Delta region, southern China

We analyze 16-month data of 13 major halocarbons measured at a southern China coastal site in the greater Pearl River Delta (PRD). A total of 188 canister air samples were collected from August 2001 to December 2002. Overall inspection indicated that CH2Cl2, C2Cl 4, and C2HCl3 had similar temporal variations while CFC-11, CFC-12, and CFC-113 showed the same emission patterns during the sampling period. Diurnal variations of halocarbons presented different patterns during ozone episode days, mainly related to emission strength, atmospheric dispersion, and photochemical lifetimes. For further statistics and source appointment, Lagrangian backward particle release simulations were conducted to help understand the potential source regions of all samples and classify them into different categories, including local Hong Kong, inner PRD, continental China, and marine air masses. With the exception of HCFC-142b, the mixing ratios of all halocarbons in marine air were significantly lower than those in urban and regional air (p < 0.01), whereas no significant difference was found between urban Hong Kong and inner PRD regional air, reflecting the dominant impact of the greater PRD regional air on the halocarbon levels. The halocarbon levels in this region were significantly influenced by anthropogenic sources, causing the halocarbon mixing ratios in South China Sea air to be higher than the corresponding background levels, as measured by global surface networks and by airborne missions such as Transport and Chemical Evolution Over the Pacific. Interspecies correlation analysis suggests that CHCl3 is mainly used as a solvent in Hong Kong but mostly as a feedstock for HCFC-22 in the inner PRD. Furthermore, CH3Cl is often used as a refrigerant and emitted from biomass/biofuel burning in the inner PRD. A positive matrix factorization receptor model was applied to the classified halocarbon samples in the greater PRD for source profiles and apportionments. Seven major sources were identified and quantified. Emissions from solvent use were the most significant source of halocarbons (71 ± 9%), while refrigeration was the second largest contributor (18 ± 2%). By further looking at samples from the inner PRD and from urban Hong Kong separately, we found that more solvent was used in the dry cleaning industry in Hong Kong, whereas the contribution of cleaning solvent in the electronic industry was higher in the inner PRD. Besides the two common sources of solvent use and refrigeration, the contributions of biomass/biofuel burning and feedstock in chemical manufacturing was remarkable in the inner PRD but negligible in Hong Kong. These findings are of help to effectively control and phase out the emissions of halocarbons in the greater PRD region of southern China Copyright 2009 by the American Geophysical Union

Carbonyl sulfide and carbon disulfide: Large-scale distributions over the western Pacific and emissions from Asia during TRACE-P

An extensive set of carbonyl sulfide (OCS) and carbon disulfide (CS2) observations were made as part of the NASA Transport and Chemical Evolution over the Pacific (TRACE-P) project, which took place in the early spring 2001. TRACE-P sampling focused on the western Pacific region but in total included the geographic region 110°E to 290°E longitude, 5°N to 50°N latitude, and 0–12 km altitude. Substantial OCS and CS2 enhancements were observed for a great many air masses of Chinese and Japanese origin during TRACE-P. Over the western Pacific, mean mixing ratios of long-lived OCS and shorter-lived CS2 showed a gradual decrease by about 10% and a factor of 5–10, respectively, from the surface to 8–10 km altitude, presumably because land-based sources dominated their distribution during February through April 2001. The highest mean OCS and CS2levels (580 and 20 pptv, respectively, based on 2.5° × 2.5° latitude bins) were observed below 2 km near the coast of Asia, at latitudes between 25°N and 35°N, where urban Asian outflow was strongest. Ratios of OCS versus CO for continental SE Asia were much lower compared to Chinese and Japanese signatures and were strongly associated with biomass burning/biofuel emissions. We present a new inventory of anthropogenic Asian emissions (including biomass burning) for OCS and CS2 and compare it to emission estimates based on regional relationships of OCS and CS2 to CO and CO2. The OCS and CS2 results for the two methods compare well for continental SE Asia and Japan plus Korea and also for Chinese CS2 emissions. However, it appears that the inventory underestimates Chinese emissions of OCS by about 30–100%. This difference may be related to the fact that we did not include natural sources such as wetland emissions in our inventory, although the contributions from such sources are believed to be at a seasonal low during the study period. Uncertainties in OCS emissions from Chinese coal burning, which are poorly characterized, likely contribute to the discrepancy