A study of surface ozone and the relation to complex wind flow in Hong Kong

Ozone measurements made from 5 sites in Hong Kong have been analyzed, including those from one upwind, one downwind, and three urban locales. The data are analyzed in terms of the seasonal and diurnal trends. A subset of data in autumn is further analyzed to study the relationship between the ozone spatial pattern and wind flow as well as other meteorological parameters. The results show that averaged ozone levels at most sites exhibit maxima in autumn, which appears to be a unique feature for eastern Asia. On average the daily maximum 1-h concentrations are found to be higher in the western (normally downwind) site than those on the eastern side and in urban areas. Examination of surface wind patterns and other meteorological parameters suggest that elevated ozone concentrations on the western side occur during the days with intense solar radiation, light winds, and in the presence of a unique wind circulation. The wind reversal in the western parts under the “convergence” flow is believed to be an important cause of the high-ozone events observed there. Such wind flow may re-circulate/transport nearby urban plumes (in this case the Hong Kong–Shenzhen urban complex). Examination of chemical data from the western site has shown that averaged afternoon SO₂ to NO_x ratios on days with wind reversal are larger than those of typical urban Hong Kong and that a significant SO₂ enhancement was clearly indicated on several occasions. The SO₂ enhancement may be interpreted as being the evidence to suggest the contribution of regional sources and/or Hong Kong’s power plants (both containing high SO₂). A case study has shown that when moderately strong northwesterly wind prevails, elevated ozone and SO₂ can be transported to western Hong Kong from the inner Pearl Delta region. This study has also indicated that under the impact of ENE winds the eastern side of Hong Kong is not frequently affected by the re-circulating ozone plumes present in the western side.     

Ground-level ozone in the Pearl River Delta region: Analysis of data from a recently established regional air quality monitoring network

The ambient air quality monitoring data of 2006 and 2007 from a recently established Pearl River Delta (PRD) regional air quality monitoring network are analyzed to investigate the characteristics of ground-level ozone in the region. Four sites covering urban, suburban, rural and coastal areas are selected as representatives for detailed analysis in this paper. The results show that there are distinct seasonal and diurnal cycles in ground-level ozone across the PRD region. Low ozone concentrations are generally observed in summer, while high O₃ levels are typically found in autumn. The O₃ diurnal variations in the urban areas are larger than those at the rural sites. The O₃ concentrations showed no statistically significant difference between weekend and weekdays in contrast to the findings in many other urban areas in the world. The average ozone concentrations are lower in urban areas compared to the sites outside urban centers. Back trajectories are used to show the major air-mass transport patterns and to examine the changes in ozone from the respective upwind sites to a site in the center of the PRD (Wanqingsha). The results show higher average ozone concentrations at the upwind sites in the continental and coastal air masses, but higher 1 h-max O₃ concentrations (by 8–16 ppbv) at the center PRD site under each of air-mass category, suggesting that the ozone pollution in the PRD region exhibits both regional and super-regional characteristics.     

Local and regional anthropogenic influence on PM2.5 elements in Hong Kong

Hong Kong's persistent unhealthy level of fine particulate matter is a current public health challenge, complicated by the city being located in the rapidly industrializing Pearl River Delta Region of China. While the sources of the region's fine particulate matter (PM_2.5) are still not well understood, this study provides new source information through ground measurements and statistical analysis of 24 elements associated with particulate matter collected on filters. Field measurements took place over 4 months (October 2002, December 2002, March 2003, and June 2003) at seven sites throughout the Pearl River Delta, with three sites located in Hong Kong and four sites in the neighboring province, Guangdong. The 4-month average element concentrations show significant variation throughout the region, with higher levels of nearly every species seen among the northern Guangdong sites in comparison to Hong Kong. The high correlation (Pearson r>0.8) and similar magnitudes of 11 species (Al, Si, S, K, Ca, Mn, Fe, Zn, Br, Rb, and Pb) at three contrasting sites in Hong Kong indicate that sources external to Hong Kong dominate the regional levels of these elements. Further correlative analysis compared Hong Kong against potential source areas in Guangdong Province (Shenzhen, Zhongshan, and Guangzhou). Moderate correlation of sulfur for all pairings of Hong Kong sites with three Guangdong sites in developed areas (average Pearson r of 0.52–0.94) supports the importance of long-distance transport impacting the region as a whole, although local sources also clearly impact observed concentrations. Varying correlative characteristics for zinc when Hong Kong sites are paired with Shenzhen (average r=0.86), Guangzhou (average r=−0.65) and Zhongshan (average r=0.45) points to a source area located south of Guangzhou and locally impacting Zhongshan. The concentration distribution and correlative characteristics of bromide point to sources located within the Pearl River Delta, but the specific location is yet inconclusive. Uniquely poor correlation of eight species (Al, Si, K, Ca, Mn, Fe, Rb, and Pb) for the pairing of Hong Kong sites with Guangzhou, in addition to the relatively higher concentrations measured at Guangzhou, indicates a significant regional impact due to land development and industrial activities in the Guangzhou vicinity.     

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.     

Characteristics and diurnal variations of NMHCs at urban,suburban, and rural sites in the Pearl River Delta and a remote site in South China

The Pearl River Delta (PRD) is one of the most industrialized and urbanized regions in China. With rapid growth of the economy, it is suffering from deteriorating air quality. Non-methane hydrocarbons (NMHCs) were investigated at urban and suburban sites in Guangzhou (GZ), a rural site in PRD and a clean remote site in South China, in April 2005. Additional roadside samples in GZ and Qingxi (QX, a small industrial town in PRD), ambient air samples at the rooftop of a printing factory in QX and exhaust samples from liquefied petroleum gas (LPG)—fueled taxis in GZ were collected to help identify the source signatures of NMHCs. A large fraction of propane (47%) was found in exhaust samples from LPG-fueled taxis in GZ and extremely high levels of toluene (2.0–3.1 ppmv) were found at the rooftop of the printing factory in QX. Vehicular and industrial emissions were the main sources of NMHCs. The effect of vehicular emission on the ambient air varied among the three PRD sites. The impact of industrial emissions was widespread and they contributed greatly to the high levels of aromatic hydrocarbons, especially toluene, at the three PRD sites investigated. Leakage from vehicles fueled by LPG contributed mainly to the high levels of propane and n-butane at the urban GZ site. Ethane and ethyne from long-range transport and isoprene from local biogenic emission were the main contributors to the total hydrocarbons at the remote site. Diurnal variations of NMHCs showed that the contribution from vehicular emissions varied with traffic conditions and were more influenced by fresh emissions at the urban site and by aged air at the suburban and rural sites. Isoprene from biogenic emission contributed largely to the ozone formation potential (OFP) at the remote site. Ethene, toluene and m/p-xylene were the main contributors to the OFP at the three PRD sites.     

Modeling and direct sensitivity analysis of biogenic emissions impacts on regional ozone formation in the Mexico-U.S. border area

A spatially and temporally resolved biogenic hydrocarbon and nitrogen oxides (NOx) emissions inventory has been developed for a region along the Mexico-U.S. border area. Average daily biogenic non-methane organic gases (NMOG) emissions for the 1700 x 1000 km2 domain were estimated at 23,800 metric tons/day (62% from Mexico and 38% from the United States), and biogenic NOx was estimated at 1230 metric tons/day (54% from Mexico and 46% from the United States) for the July 18-20, 1993, ozone episode. The biogenic NMOG represented 74% of the total NMOG emissions, and biogenic NOx was 14% of the total NOx. The CIT photochemical airshed model was used to assess how biogenic emissions impact air quality. Predicted ground-level ozone increased by 5-10 ppb in most rural areas, 10-20 ppb near urban centers, and 20-30 ppb immediately downwind of the urban centers compared to simulations in which only anthropogenic emissions were used. A sensitivity analysis of predicted ozone concentration to emissions was performed using the decoupled direct method for three dimensional air quality models (DDM-3D). The highest positive sensitivity of ground-level ozone concentration to biogenic volatile organic compound (VOC) emissions (i.e., increasing biogenic VOC emissions results in increasing ozone concentrations) was predicted to be in locations with high NOx levels, (i.e., the urban areas). One urban center--Houston--was predicted to have a slight negative sensitivity to biogenic NO emissions (i.e., increasing biogenic NO emissions results in decreasing local ozone concentrations). The highest sensitivities of ozone concentrations to on-road mobile source VOC emissions, all positive, were mainly in the urban areas. The highest sensitivities of ozone concentrations to on-road mobile source NOx emissions were predicted in both urban (either positive or negative sensitivities) and rural (positive sensitivities) locations.     

Evaluation of ozone-nitrogen oxides-volatile organic compound sensitivity of Cincinnati, Ohio

Ambient concentrations of ozone (O3), nitrogen oxides (NOx), total reactive nitrogen (NOy), nitric acid (HNO3), and hydrogen peroxide (H2O2) were measured during September 2003 at an urban site of Cincinnati, OH. The aim of this study was two-fold: to investigate whether O3 formation in this population exposure-type site is NOx, sensitive or volatile organic compound (VOC) sensitive and to test the practicality of using two combined observational-based methods to identify the sensitivity of O3 formation in midlevel polluted locations. The evaluation of the indicator species: NOy, O3/NOy, O3/HNO3, H2O2/ HNO3, and O3/(estimated NOx reaction products), as well as the combined hypothesis testing analysis of the weekend/weekday (WE/WD) differences of 1-hr and 8-hr average maximum O3 and of the 6:00 a.m.-9:00 a.m. average nitric oxide and NOx concentrations, show evidence that Cincinnati is likely VOC sensitive. Average WE 1-hr and 8-hr maximum O3, as well as duration of WE O3 accumulation, were not lower than the corresponding WD levels in spite of the observed significant reduction in NO, emissions on WE, a typical situation in VOC-sensitive locations. The possibility that the seasonal transition from summer to autumn could have influenced the results was also investigated through an exploratory analysis of the afternoon O3 maximum/NOx measured and of the WE/WD differences of peak O3 and morning average NO and NO, concentrations observed at this site from June through September 2003. The results suggest that a VOC-sensitive chemistry regime dominated along the summer season. The findings of this study suggest that additional reductions in regional NO, emissions in Cincinnati, a potential nonattainment area under the 8-hr O3 standard, may cause an increase in local O3. Future strategies to reduce O3 in Southwest Ohio should be further evaluated carefully. The combination of observational-based methods might provide a consistent complementary approach in the identification of the NO,-VOC sensitive characteristics of mid-to-moderate polluted urban areas.     

Analyses of ozone in urban and rural sites in Málaga (Spain)

Ozone concentrations were measured at two (urban and a rural) sites near the city of Málaga (Spain). The aim of this study was to determine the daily, monthly and seasonal variation patterns of ozone concentrations at both sites and to study the possible regional influences. The daily variations mostly have the usual features with the afternoon maximum and the night minimum being more pronounced in the urban area. The average monthly concentrations throughout the year start to increase in March reaching their maximum values in July for the urban site. However, in the rural area, the monthly variations are smaller reaching their maximum value in June. The hourly evolution of the ozone concentrations in both sampling sites is well defined in spring and summer and not so well defined in autumn and winter. Taking into account the four seasons, the rural concentrations are higher than the urban ones. Summer is the season when there are similar concentrations at both sampling sites. Average hourly summer afternoon ozone for the hours 12:00-20:00 LST exceeded the 110 microg m(-3) European Union guidelines for human health for 8 h ozone exposure at the urban and rural sites.     

Comparative assessment of ambient air quality in two typical Mediterranean coastal cities in Greece

Air quality data (O3, NO2, NO, CO and SO2) of two Greek coastal cities, Patras and Volos, were analyzed and compared to evaluate: (a) the exceedances of air quality EU threshold values, (b) the diurnal patterns of air pollutants and (c) the "weekend effect" on ozone levels. High ozone levels, close to the thresholds for human health and clearly above the threshold for the protection of plants and ecosystems, were observed in Volos. O3 levels in Volos were higher than those in Patras. NOx levels in Patras were significantly higher than the limits for human health and plants' protection. Both, NOx and SO2 levels were higher in Patras than in Volos. The Patras' harbor high traffic seems to drive the diurnal pattern of SO2 in that city. The examination of the rate of ozone accumulation, during the high O3 period (Apr.-Sep.), revealed the occurrence of two phases, a fast and a slow one, with different durations in each city. We suggest that the occurrence of such two phases' patterns should be considered in relevant ozone studies. In both towns, the O3 levels were higher during weekends in comparison to midweek days, although NO levels were lower. Our results support the hypothesis that the weekend O3 effect is due to a combination of VOC sensitivity of the studied areas and the reduced NOx emissions during weekends. Based on the comparison of the weekend effect in the two cities, we suggest the occurrence of a feedback mechanism between peri-urban natural ecosystems (forests) and the polluting anthropogenic ones (cities).     

Regional variations in sulfate and nitrate on annual, seasonal, and synoptic time scales

Ambient data from Interagency Monitoring of Protected Visual Environments (IMPROVE) monitors are analyzed to evaluate the spatial structure of SO4 and NO3 aerosols in the mid-Atlantic region. Sub-weekly, seasonal, and annual data values are compared between the IMPROVE Washington, DC, site and three rural sites. Synoptic perturbations are compared between sites to quantify similarities in short-term temporal perturbations of SO4 and NO3. Based on these comparisons between the rural and urban IMPROVE monitors, the spatial structure of SO4 shows broad regional homogeneity that is recognizable from both the long-term average values and the short-term variations. NO3 data on a seasonal and annual basis show much larger spatial gradients between the urban Washington monitor and the three rural monitors than do SO4 data. Short-term NO3 perturbations at the three rural monitors also differ significantly from those at the Washington site. These dissimilarities in NO3 levels between the rural and urban IMPROVE monitors on both short-term and longer-term time scales indicate little homogeneity of NO3 aerosols in the mid-Atlantic region considered here. The volatility of NO3 aerosols and the removal rate of HNO3 via dry deposition could contribute to the spatial variability differences shown here between SO4 and NO3.     

Sources and characteristics of carbonaceous aerosol in two largest cities in Pearl River Delta Region,China

PM_2.5 samples were collected at five sites in Guangzhou and Hong Kong, Pearl River Delta Region (PRDR), China in both summer and winter during 2004–2005. Elemental carbon (EC) and organic carbon (OC) in these samples were measured. The OC and EC concentrations ranked in the order of urban Guangzhou > urban Hong Kong > background Hong Kong. Total carbonaceous aerosol (TCA) contributed less to PM_2.5 in urban Guangzhou (32–35%) than that in urban Hong Kong (43–57%). The reason may be that, as an major industrial city in South China, Guangzhou would receive large amount of inorganic aerosol from all kinds of industries, however, as a trade center and seaport, urban Hong Kong would mainly receive organic aerosol and EC from container vessels and heavy-duty diesel trucks. At Hong Kong background site Hok Tsui, relatively lower contribution of TCA to PM_2.5 may result from contributions of marine inorganic aerosol and inland China pollutant. Strong correlation (R²=0.76–0.83) between OC and EC indicates minor fluctuation of emission and the secondary organic aerosol (SOA) formation in urban Guangzhou. Weak correlation between OC and EC in Hong Kong can be related to the impact of the long-range transported aerosol from inland China. Averagely, secondary OC (SOC) concentrations were 3.8–5.9 and 10.2–12.8 μg m⁻³, respectively, accounting for 21–32% and 36–42% of OC in summer and winter in Guangzhou. The average values of 4.2–6.8% for SOA/ PM_2.5 indicate that SOA was minor component in PM_2.5 in Guangzhou.     

Use of stationary and mobile measurements to study power plant emissions

This paper presents a technique to study air pollution by combining high spatial resolution data obtained by a mobile platform and those measured by conventional stationary stations. Conventional stations provide time-series point data but cannot yield information that is distant from the sites. This can be complemented or supplemented by mobile measurements in the vicinity of the conventional sites. Together, the combined dataset yields a clearer and more precise picture of the dispersion and the transformation of pollutants in the atmosphere in a fixed time frame. Several experiments were conducted in the years 2002-2003 to track the impact of power plant plumes on ground receptors in the immediate vicinity (within a radius of 30 km) of the plants, using a combined mobile and stationary dataset. The mobile data allowed the identification of emissions from coal-fired and gas-fired power plants. Coal-fired power plants were the major source of sulfur dioxide (SO2), whereas nitrogen oxides (NOx) emitted from the gas-fired power plant played an important role in the formation of ozone (O3) at ground level. The mobile data showed that two particle size distribution regimes were detected: one had a dominant accumulation mode at 0.40-0.65 microm and the other at 0.65-1 microm. The existence of particles characterized by their mode at 0.65-1 microm and formed by in-cloud processes suggests that vehicular emissions were not the important source. Other local sources, such as power plants (elevated emission), were the likely sources, because Hong Kong does not have much manufacturing industry.     

Understanding the effectiveness of precursor reductions in lowering 8-hr ozone concentrations--Part II. The eastern United States

Analyses of ozone (O3) measurements in conjunction with photochemical modeling were used to assess the feasibility of attaining the federal 8-hr O3 standard in the eastern United States. Various combinations of volatile organic compound (VOC) and oxides of nitrogen (NOx) emission reductions were effective in lowering modeled peak 1-hr O3 concentrations. VOC emissions reductions alone had only a modest impact on modeled peak 8-hr O3 concentrations. Anthropogenic NOx emissions reductions of 46-86% of 1996 base case values were needed to reach the level of the 8-hr standard in some areas. As NOx emissions are reduced, O3 production efficiency increases, which accounts for the less than proportional response of calculated 8-hr O3 levels. Such increases in O3 production efficiency also were noted in previous modeling work for central California. O3 production in some urban core areas, such as New York City and Chicago, IL, was found to be VOC-limited. In these areas, moderate NOx emissions reductions may be accompanied by increases in peak 8-hr O3 levels. The findings help to explain differences in historical trends in 1- and 8-hr O3 levels and have serious implications for the feasibility of attaining the 8-hr O3 standard in several areas of the eastern United States.     

Interval estimation of urban ozone level and selection of influential factors by employing automatic relevance determination model

In this work, we focus on simulating the ground-level ozone (O3) time series and its daily maximum concentration in Hong Kong urban air by employing the multilayer perceptron (MLP) model combined with the automatic relevance determination (ARD) method (for simplicity, we name it as MLP-ARD model). Two air quality monitoring sites in Hong Kong, i.e., Tsuen Wan and Tung Chung, are selected for the numerical experiments. The MLP-ARD model based on Bayesian evidence framework can provide reliable interval estimation of real observation as well as offering efficient strategy to avoid over-fitting. The performance comparisons between MLP-ARD model and traditional artificial neural network (ANN) model based on maximum likelihood indicate that MLP-ARD model is more powerful to capture the wild fluctuation of O3 level especially during O3 episodes than the traditional model. Furthermore, it can assess and rank the input variables for the prediction according to their relative importance to the output variable, i.e., the daily maximum O3 concentration in this study. The preliminary experimental results indicate that nitric oxide (NO) and solar radiation are the most important input variables for O3 prediction at both selected sites. In addition, the previous daily maximum O3 level is also important for Tung Chung site. In this regard, MLP-ARD model is a feasible tool to interpret the real physical and chemical process of urban O3 variation.     

Long-term variation in surface ozone and its precursors in Athens,Greece

INTENTION, GOAL, SCOPE, BACKGROUND: Photochemical pollution is a very complex process involving meteorological, topographic, emission and chemical parameters. The most important chemical mechanisms involved in the atmospheric process have already been identified and studied. However, many unknown parameters still exist because of the large number of participating chemical reactions. OBJECTIVE: The present study investigates the processes involved in the photochemical pollution effect of an urban station located in the greater area of the Athens basin and gives a plausible explanation for the different seasonal ozone development between that station and another rural one. Furthermore, the distribution of the mean monthly surface ozone observed at the urban station during 1987-2001 is examined in order to create a relevant forecasting tool. METHODS: Averaged hourly data of O3 and NOx observations monitored at the above mentioned stations, during 1987-2001, have been used in order to derive the daytime (7:00-15:00) values. Trajectories calculated by using a 2D-trajectory code and meteorological data, during the period 1988-1996, have also been used. RESULTS AND DISCUSSION: At the urban station, the percentage negative trend of NO and NOx data in winter and summer is higher than that in spring and autumn, while the percentage ozone trend is maximum in the summer. On the contrary, the negative surface ozone trend at the rural station exhibits a minimum in summer and a maximum in autumn and winter. The mean seasonal wind-rose for the selected months shows that the northward wind flow dominates during June, the month of the lowest negative ozone trend in the rural station. Finally, the development of the forecasting tool shows that the mean monthly surface ozone data during the period (1987-2001) demonstrates a semi-log distribution. CONCLUSIONS: Air transport effect on the air pollution of the rural station (not blocked by mountains) is deduced as a possible reason for the different seasonal ozone development observed between the rural and the urban station. Finally, the discrepancies between the theoretical probabilities deduced by the model and the empirical ones appear to be very small, and the corresponding correlation coefficient is 0.99. RECOMMENDATION AND OUTLOOK: However, to interpret the aforementioned statistical results about the negative trends in ozone and its precursors, additional parameters can be taken into account. Changes in NOx concentrations, for instance, can result not only from changes in emissions or meteorological conditions. There might also be a contribution through changes in the atmospheric composition. A study of the contribution of changes in atmospheric composition to trends of observed NOx concentrations requires that a series of steps be taken (removal of meteorological influence in the time series, calculation of trends in OH concentrations, etc.).     

Estimating long-term population exposure to ozone in urban areas of Europe

Tropospheric ozone concentrations regarded as harmful for human health are frequently encountered in Central Europe in summertime. Although ozone formation generally results from precursors transported over long distances, in urban areas local effects, such as reactions due to nearby emission sources, play a major role in determining ozone concentrations. Europe-wide mapping and modeling of population exposure to high ozone concentrations is subject to many uncertainties, because small-scale phenomena in urban areas can significantly change ozone levels from those of the surroundings. Currently the integrated assessment modeling of European ozone control strategies is done utilizing the results of large-scale models intended for estimating the rural background ozone levels. This paper presents an initial study on how much local nitrogen oxide (NOx) concentrations can explain variations between large-scale ozone model results and urban ozone measurements, on one hand, and between urban and nearby rural measurements, on the other. The impact of urban NOx concentrations on ozone levels was derived from chemical equations describing the ozone balance. The study investigated the applicability of the method for improving the accuracy of modeled population exposure, which is needed for efficient control strategy development. The method was tested with NOx and ozone measurements from both urban and rural areas in Switzerland and with the ozone predictions of the large-scale photochemical model currently used in designing Europe-wide control strategies for ground-level ozone. The results suggest that urban NOx levels are a significant explanatory factor in differences between urban and nearby rural ozone concentrations and that the phenomenon could be satisfactorily represented with this kind of method. Further research efforts should comprise testing of the method in more locations and analyzing the performance of more widely applicable ways of deriving the initial parameters.     

Receptor modeling of source apportionment of Hong Kong aerosols and the implication of urban and regional contribution

Understanding the spatial–temporal variations of source apportionment of PM_2.5 is critical to the effective control of particulate pollution. In this study, two one-year studies of PM_2.5 composition were conducted at three contrasting sites in Hong Kong from November 2000 to October 2001, and from November 2004 to October 2005, respectively. A receptor model, principal component analysis (PCA) with absolute principal component scores (APCS) technique, was applied to the PM_2.5 data for the identification and quantification of pollution sources at the rural, urban and roadside sites. The receptor modeling results identified that the major sources of PM_2.5 in Hong Kong were vehicular emissions/road erosion, secondary sulfate, residual oil combustion, soil suspension and sea salt regardless of sampling sites and sampling periods. The secondary sulfate aerosols made the most significant contribution to the PM_2.5 composition at the rural (HT) (44 ± 3%, mean ± 1σ standard error) and urban (TW) (28 ± 2%) sites, followed by vehicular emission (20 ± 3% for HT and 23 ± 4% for TW) and residual oil combustion (17 ± 2% for HT and 19 ± 1% for TW). However, at the roadside site (MK), vehicular emissions especially diesel vehicle emissions were the major source of PM_2.5 composition (33 ± 1% for diesel vehicle plus 18 ± 2% for other vehicles), followed by secondary sulfate aerosols (24 ± 1%). We found that the contribution of residual oil combustion at both urban and rural sites was much higher than that at the roadside site (2 ± 0.4%), perhaps due to the marine vessel activities of the container terminal near the urban site and close distance of pathway for the marine vessels to the rural site. The large contribution of secondary sulfate aerosols at all the three sites reflected the wide influence of regional pollution. With regard to the temporal trend, the contributions of vehicular emission and secondary sulfate to PM_2.5 showed higher autumn and winter values and lower summer levels at all the sites, particularly for the background site, suggesting that the seasonal variation of source apportionment in Hong Kong was mainly affected by the synoptic meteorological conditions and the long-range transport. Analysis of annual patterns indicated that the contribution of vehicular emission at the roadside was significantly reduced from 2000/01 to 2004/05 (p < 0.05, two-tail), especially the diesel vehicular emission (p < 0.001, two-tail). This is likely attributed to the implementation of the vehicular emission control programs with the tightening of diesel fuel contents and vehicular emission standards over these years by the Hong Kong government. In contrast, the contribution of secondary sulfate was remarkably increased from 2001 to 2005 (p < 0.001, two-tail), indicating a significant growth in regional sulfate pollution over the years.     

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.     

Measurements of nitrogen dioxide concentrations at rural sites in the United Kingdom using diffusion tubes

Nitrogen dioxide concentrations have been measured at rural sites in the United Kingdom and have revealed a marked spatial variation. The annual mean NO2 concentration varies from approximately 1 microg Nm-3 in Northern Ireland to approximately 7 microg Nm-3 in East Anglia. Though the temporal resolution of the diffusion tube method is limited by exposure periods of 2-4 weeks, it was possible to detect a marked seasonal variation in NO2 concentration at all sites, with higher values in the winter than in the summer. This is in contrast to the small seasonal variation previously observed at sites in London. Sulphur dioxide concentrations were measured daily using a bubbler method and, if expressed in terms of mass of sulphur and nitrogen, the SO2 and NO2 annual mean concentrations were similar. This is in contrast to an S/N ratio of greater than 3 in total UK emissions of SO2 and NOx. It seems likely that this difference is due to a combination of the different spatial distributions and heights of emissions of SO2 and NOx, the influence of local sources of NOx, and the smaller S/N ratio in Continental European emissions.     

Ozone air quality over North America: part I--a review of reported trends

Ozone and precursor trends can be used to measure the effectiveness of regulatory programs that have been implemented. In this paper, we review trends in the concentrations of O3 NOx, and HCs over North America that have been reported in the literature. Although most existing trend studies are confounded by meteorological variability, both the raw data trends and the trends adjusted for meteorology collectively indicate a general decreasing trend in O3 concentrations in most areas of the United States during 1985-1996. In Canada, mean daily maximum 1-hr O3 concentrations at urban sites show mixed trends with a majority of sites showing an increase from 1980 to 1993. Mean daily maximum 1-hr O3 at most regionally representative Canadian sites appears to decrease from 1985 to 1993 or shows no significant change. There are far fewer data and analyses of NOx and HC trends. Available studies covering various ranges of years indicate decreases in ambient NO and HC concentrations in Los Angeles, CA, decreases in HC concentrations in northeastern U.S. cities, and decreases in NOx concentrations in Canadian cities. Two key needs are long-term HC and NOx measurements, particularly at rural sites, and a systematic comparison of trend detection techniques on a reference data set.