Assessing photochemical ozone formation in the Pearl River Delta with a photochemical trajectory model

A photochemical trajectory model (PTM), coupled with the Master Chemical Mechanism (MCM) describing the degradation of 139 volatile organic compounds (VOCs) in the troposphere, was developed and used for the first time to simulate the formation of photochemical pollutants at Wangqingsha (WQS), Guangzhou during photochemical pollution episodes between 12 and 17 November, 2007. The simulated diurnal variations and mixing ratios of ozone were in good agreement with observed data (R2=0.80, P<0.05), indicating that the photochemical trajectory model - an integration of boundary layer trajectories, precursor emissions and chemical processing - provides a reasonable description of ozone formation in the Pearl River Delta (PRD) region. Calculated photochemical ozone creation potential (POCP) indices for the region indicated that alkanes and oxygenated organic compounds had relatively low reactivity, while alkenes and aromatics presented high reactivity, as seen in other airsheds in Europe. Analysis of the emission inventory found that the sum of 60 of the 139 VOC species accounted for 92% of the total POCP-weighted emission. The 60 VOC species include C2-C6 alkenes, C6-C8 aromatics, biogenic VOCs, and so on. The results indicated that regional scale ozone formation in the PRD region can be mainly attributed to a relatively small number of VOC species, namely isoprene, ethene, m-xylene, and toluene, etc. A further investigation of the relative contribution of the main emission source categories to ozone formation suggested that mobile sources were the largest contributor to regional O3 formation (40%), followed by biogenic sources (29%), VOC product-related sources (23%), industry (6%), biomass burning (1%), and power plants (1%). The findings obtained in this study would advance our knowledge of air quality in the PRD region, and provide useful information to local government on effective control of photochemical smog in the region. © 2010 Elsevier Ltd

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

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

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

Estimation of Age-at-Death for Adult Males Using the Acetabulum, Applied to Four Western European Populations *

Peer Reviewedhttp://deepblue.lib.umich.edu/bitstream/2027.42/73732/1/j.1556-4029.2007.00486.x.pd

Toward High-Precision Measures of Large-Scale Structure

I review some results of estimation of the power spectrum of density fluctuations from galaxy redshift surveys and discuss advances that may be possible with the Sloan Digital Sky Survey. I then examine the realities of power spectrum estimation in the presence of Galactic extinction, photometric errors, galaxy evolution, clustering evolution, and uncertainty about the background cosmology.Comment: 24 pages, including 11 postscript figures. Uses crckapb.sty (included in submission). To appear in ``Ringberg Workshop on Large-Scale Structure,'' ed D. Hamilton (Kluwer, Amsterdam), p. 39