Control of Ozone Precursors in a Complex Industrial Terrain by Using Multiscale-Nested Air Quality Models with Fine Spatial Resolution (1 km2)

Abstract

The location of the northeastern Iberian Peninsula (NEIP) in the northwestern Mediterranean basin, the presence of the Pyrenees mountain range (with altitudes >3000 m), and the influence of the Mediterranean Sea and the large valley canalization of Ebro river induce an extremely complicated structure for the dispersion of photochemical pollutants. Air pollution studies in very complex terrains such as the NEIP require high-resolution modeling for resolving the very complex dynamics of flows. To deal with the influence of larger-scale transport, however, high-resolution models have to be nested in larger models to generate appropriate initial and boundary conditions for the finer resolution domains. This article shows the results obtained through the utilization of the MM5-EMICAT2000-CMAQ multiscale-nested air quality model relating the sensitivity regimes for ozone (O₃)-nitrogen oxides (NO_x)-volatile organic compounds (VOCs) in an area of high geographical complexity, like the industrial area of Tarragona, located in the NEIP. The model was applied with fine temporal (one-hour) and spatial resolution (cells of 24 km, 2 km, and 1 km) to represent the chemistry and transport of tropospheric O₃ and other photochemical species with respect to different hypothetical scenarios of emission controls and to quantify the influence of different emission sources in the area. Results indicate that O₃ chemistry in the industrial domain of Tarragona is strongly sensitive to VOCs; the higher percentages of reduction for ground-level O₃ are achieved when reducing by 25% the emissions of industrial VOCs. On the contrary, reductions in the industrial emissions of NO_x contribute to a strong increase in hourly peak levels of O₃. At the same time, the contribution of on-road traffic and biogenic emissions to ground-level O₃ concentrations in the area is negligible with respect to the pervasive weight of industrial sources. This analysis provides an assessment of the effectiveness of different policies for the control of emission of precursors by comparing the modeled results for different scenarios.     

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.     

An environmental decision-making tool for evaluating ground-level ozone-related health effects

A computer model called the Ozone Risk Assessment Model (ORAM) was developed to evaluate the health effects caused by ground-level ozone (O3) exposure. ORAM was coupled with the U.S. Environmental Protection Agency's (EPA) Third-Generation Community Multiscale Air Quality model (Models-3/CMAQ), the state-of-the-art air quality model that predicts O3 concentration and allows the examination of various scenarios in which emission rates of O3 precursors (basically, oxides of nitrogen [NOx] and volatile organic compounds) are varied. The principal analyses in ORAM are exposure model performance evaluation, health-effects calculations (expected number of respiratory hospital admissions), economic valuation, and sensitivity and uncertainty analysis through a Monte Carlo simulation. As a demonstration of the system, ORAM was applied to the eastern Tennessee region, and the entire O3 season was simulated for a base case (typical emissions) and three different emission scenarios. The results indicated that a synergism occurs when reductions in NOx emissions from mobile and point sources were applied simultaneously. A 12.9% reduction in asthma hospital admissions is expected when both mobile and point source NOx emissions are reduced (50 and 70%, respectively) versus a 5.8% reduction caused by mobile source and a 3.5% reduction caused by point sources when these emission sources are reduced individually.     

Methodologies for estimating disaggregated anthropogenic emissions--application to a coastal Mediterranean region of Spain

Regional estimates of both anthropogenic and biogenic emissions are important inputs for models of atmospheric chemistry. A disaggregated emissions inventory of all relevant pollutants for an area of 100 x 100 km2 centered in Burriana (Castellon, Spain) has been worked out. Time and spatial resolutions were hourly and 1 x 1 km2, respectively. Estimates were made for all relevant sources of anthropogenic emissions. The pollutants considered were SO2, NOx, NMVOCs (nonmethane volatile organic compounds), CH4, CO, CO2, N2O, and NH3. Thus, the emissions inventory includes up to 18 different NMVOCs. Emissions were computed for a typical sunny workday in June when strong photochemical activity could be expected. A "top-down" methodology was applied, taking as a starting point official annual and provincial estimates based on CORINAIR emission factors. This procedure is a very useful tool, particularly for those cases where a lack of sufficient local detailed information about the main emission-generating activities, such as road traffic, makes the use of a "bottom-up" approximation inadvisable. Moreover, updating these emission inventories is easier and they could be used to evaluate the impact of possible abatement strategies.     

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.     

Air quality modeling of interpollutant trading for ozone precursors in an urban area

Emission trading is a market-based approach designed to improve the efficiency and economic viability of emission control programs; emission trading has typically been confined to trades among single pollutants. Interpollutant trading (IPT), as described in this work, allows for trades among emissions of different compounds that affect the same air quality end point, in this work, ambient ozone (O3) concentrations. Because emissions of different compounds impact air quality end points differently, weighting factors or trading ratios (tons of emissions of nitrogen oxides (NO(x)) equivalent to a ton of emissions of volatile organic compounds [VOCs]) must be developed to allow for IPT. In this work, IPT indices based on reductions in O3 concentrations and based on reductions in population exposures to O3 were developed and evaluated using a three-dimensional gridded photochemical model for Austin, TX, a city currently on the cusp of nonattainment with the National Ambient Air Quality Standards for O3 concentrations averaged over 8 hr. Emissions of VOC and NO(x) from area and mobile sources in Austin are larger than emissions from point sources. The analysis indicated that mobile and area sources exhibited similar impacts. Trading ratios based on maximum O3 concentration or population exposure were similar. In contrast, the trading ratios did exhibit significant (more than a factor of two) day-to-day variability. Analysis of the air quality modeling indicated that the daily variability in trading ratios could be attributed to daily variations in both emissions and meteorology.     

Modeling weekday/weekend ozone differences in the Los Angeles region for 1997

Numerous studies of ambient ozone (O3) in the Los Angeles (LA) area have found both increases and decreases in elevated O3 levels on weekends, depending on location and year. Since the mid-1990s, average daily maximum O3 levels have been higher on weekends than on weekdays throughout most of the area. We used the Comprehensive Air-Quality Model with extensions to investigate causes of weekday/weekend O3 differences in the LA area for August 3-7, 1997, from the Southern California Ozone Study. Weekday/weekend emission changes were estimated, because explicit weekend inventories are not yet available from regulatory agencies. Changes to on-road motor vehicle (MV) emissions were derived from observed weekday/weekend traffic differences. The estimated changes in MV emissions of nitrogen oxides (NOx) were a 5% increase on Friday, a 27% decrease on Saturday, and a 37% decrease on Sunday, relative to Monday-Thursday levels. The corresponding changes in MV volatile organic carbon (VOC) emissions were an 8% increase on Friday, an 8% decrease on Saturday, and a 15% decrease on Sunday. Modeling these MV emissions changes explained the observed weekend O3 effect very well. Furthermore, changes to the mass of MV NOx emissions were the main contributor to O3 differences rather than changes to the timing of MV emissions. Ozone increases on weekends were caused by NOx emission decreases, because O3 formation is strongly VOC-limited throughout most of the LA area.     

Weekday versus weekend activity patterns for ozone precursor emissions in California's South Coast Air Basin

Ambient O3 concentrations in California's South Coast Air Basin (SoCAB) can be as much as 55% higher on weekends than on weekdays under comparable meteorological conditions. This is paradoxical because emissions of O3 precursors (hydrocarbons, CO, and nitrogen oxides [NOx]) are lower on weekends. Day-of-week emissions activity data were collected and analyzed to investigate the hypothesized causes of the "weekend O3 effect." Emission activity data were collected for various mobile, area, and point sources throughout the SoCAB, including on-road vehicles, lawn and garden equipment, barbecues, fireplaces, solvent use, and point sources with continuous emission monitoring data. The results of this study indicate significant differences between weekday and weekend emission activity patterns and emissions. Their combined effect results in a 12-18% decrease in reactive organic gases (ROGs) and a 35-41% decrease in NOx emissions on Saturdays and Sundays, respectively, relative to weekdays in summer 2000. These changes in emissions result in an increase of more than 30% in the ROG/NOx ratio on weekends compared with weekdays, which, along with lower NOx emissions, leads to increased O3 production on weekends.     

Estimations of real-world N2O emissions from road vehicles by means of measurements in a traffic tunnel

Ambient air measurements of N2O, NOx, CO, and HC based on grab sampling were conducted in a major traffic tunnel in Sweden, that carries up to 4,000 vehicles per hour, in order to estimate real-world emissions of N2O for road traffic. Two different methods--relative and mass balance-were used to calculate a N2O emission factor for the mixed vehicle fleet, which gave an average emission factor, at average speeds of 30-70 km/h, of approximately 25 mg N2O/ km, with a range of 7-56 mg/km.     

Photochemical smog modeling for assessment of potential impacts of different management strategies on air quality of the Bangkok Metropolitan Region, Thailand

A photochemical smog model system, the Variable-Grid Urban Airshed Model/Systems Applications International Mesoscale Model (UAM-V/SAIMM), was used to investigate photochemical pollution in the Bangkok Metropolitan Region (BMR). The model system was first applied to simulate a historical photochemical smog episode of two days (January 13-14, 1997) using the 1997 anthropogenic emission database available at the Pollution Control Department and an estimated biogenic emission. The output 1-hr ozone (O3) for BMR, however, did not meet the U.S. Environmental Protection Agency suggested performance criteria. The simulated minimum and maximum O3 values in the domain were much higher than the observations. Multiple model runs with different precursor emission reduction scenarios showed that the best model performance with the simulated 1-hr O3 meeting all the criteria was obtained when the volatile organic compound (VOC) and oxides of nitrogen (NOx) emission from mobile source reduced by 50% and carbon monoxide by 20% from the original database. Various combinations of anthropogenic and biogenic emissions in Bangkok and surrounding provinces were simulated to assess the contribution of different sources to O3 pollution in the city. O3 formation in Bangkok was found to be more VOC-sensitive than NOx-sensitive. To attain the Thailand ambient air quality standard for 1-hr O3 of 100 ppb, VOC emission in BMR should be reduced by 50-60%. Management strategies considered in the scenario study consist of Stage I, Stage II vapor control, replacement of two-stroke by four-stroke motorcycles, 100% compressed natural gas bus, 100% natural gas-fired power plants, and replacement of methyltertiarybutylether by ethanol as an additive for gasoline.     

Urban emissions measured with aircraft

Detailed knowledge of the quantity and composition of urban emissions is a prerequisite for successful application of atmospheric models to predict transport and distribution of primary and secondary air pollutants in the troposphere. We investigate the prospects and limitations of aircraft measurements in the determination of emission fluxes from urban areas. Our analysis focuses on data collected in September 1994 in and around Athens, Greece. Generally, emission fluxes from cities can be quantified with aircraft and with the minimum acceptable precision (uncertainty better than a factor of 2) only under very favorable meteorological conditions, namely in a homogeneous flow field in a well-mixed boundary layer. Better accuracy can be achieved only through ensemble averaging of repeated measurements. From our measurements in the Athens area, we deduced relative emission ratios of pollutant gases. With the support of ground-based measurements in a street canyon, the emission ratios NOx/CO, SO2/CO, and volatile organic compounds/CO (34 individual VOCs) could be determined with high precision. These results are very useful in analyzing differences between various existing emission inventories. Our data for VOCs reveal that the non-traffic emissions are of the same magnitude as the emissions originating from traffic.     

Diurnal and weekday variations in the source contributions of ozone precursors in California's South Coast Air Basin

For at least 30 years, ozone (O3) levels on weekends in parts of California's South Coast (Los Angeles) Air Basin (SoCAB) have been as high as or higher than on weekdays, even though ambient levels of O3 precursors are lower on weekends than on weekdays. A field study was conducted in the Los Angeles area during fall 2000 to test whether proposed relationships between emission sources and ambient nonmethane hydrocarbon (NMHC) and oxides of nitrogen (NOx) levels can account for observed diurnal and day-of-week variations in the concentration and proportions of precursor pollutants that may affect the efficiency and rate of O3 formation. The contributions to ambient NMHC by motor vehicle exhaust and evaporative emissions, estimated using chemical mass balance (CMB) receptor modeling, ranged from 65 to 85% with minimal day-of-week variation. Ratios of ambient NOx associated with black carbon (BC) to NOx associated with carbon monoxide (CO) were approximately 1.25 +/- 0.22 during weekdays and 0.76 +/- 0.07 and 0.52 +/- 0.07 on Saturday and Sunday, respectively. These results demonstrate that lower NOx emissions from diesel exhaust can be a major factor causing lower NOx mixing ratios and higher NMHC/NOx ratios on weekends. Nonmobile sources showed no significant day-of-week variations in their contributions to NMHC. Greater amounts of gasoline emissions are carried over on Friday and Saturday evenings but are, at most, a minor factor contributing to higher NMHC/NOx ratios on weekend mornings.     

Evaluation of total volatile organic compound emissions from adhesives based on chamber tests

In 1997, Homeswest in western Australia and Murdoch University developed a project to construct low-allergen houses (LAHs) in a newly developed suburb. Before the construction of LAHs, all potential volatile organic compound (VOC) emission materials used in LAHs are required to be measured to ensure that they are low total VOC (TVOC) emission materials. This program was developed based on this purpose. In recent times, the number of complaints about indoor air pollution caused by VOCs has increased. A number of surveys of indoor VOCs have indicated that many indoor materials contribute to indoor air pollution. Although some studies have been conducted on the characteristics of VOC emissions from adhesives, most of them were focused on VOC emissions from floor adhesives. Few measurements of VOC emissions from adhesives used for wood, fabrics, and leather are available. Furthermore, most research on VOC emissions from adhesives has been done in countries with cool climates, where ventilation rates in the indoor environment are lower than those in Mediterranean climates, due to energy conservation. VOCs emitted from adhesives have not been sufficiently researched to prepare an emission inventory to predict indoor air quality and to determine both exposure levels for the Australian population and the most appropriate strategies to reduce exposure. An environmental test chamber with controlled temperature, relative humidity, and airflow rate was used to evaluate emissions of TVOCs from three adhesives used frequently in Australia. The quantity of TVOC emissions was measured by a gas chromatography/flame ionization detector. The primary VOCs emitted from each adhesive were detected by gas chromatography/mass spectrometry. The temporal change of TVOC concentrations emitted from each adhesive was tested. A double-exponential equation was then developed to evaluate the characteristics of TVOC emissions from these three adhesives. With this double-exponential model, the physical processes of TVOC emissions can be explained, and a variety of emission parameters can be calculated. These emission parameters could be used to estimate real indoor TVOC concentrations in Mediterranean climates.     

Comparison of two photochemical modeling systems in a tropical urban area

Two photochemical smog modeling systems, UAM-V/ SAIMM (the Variable-Grid UAM/Systems Applications International Mesoscale Model) and CHIMERE/ECMWF (European Center for Medium Range Weather Forecast), are applied to the same tropical domain (Bangkok Metropolitan Region) and the same episode (January 13-14, 1997) to evaluate their relative performance using the same anthropogenic emission database (emission database available at the Pollution Control Department [PCD] 1997). Ozone (O3) produced by both models meets U.S. Environment Protection Agency (EPA) suggested prediction criteria of mean normalized bias error and mean normalized gross error on January 14 but none on January 13. Both models are tested with various modified databases of precursors emissions from the PCD original database. Performance of UAM-V is the best when using the modified emission data with volatile organic compound (VOC), NOx, and CO mobile source emission reduced by 50%, 50%, and 20% from the original database. CHIMERE suggests a similar emission database except for the VOC emission, which is a reduction by 40% from the original PCD mobile source emission. Spatial and temporal variations of O3, CO, NOy (total reactive nitrogen), and Ox (NO2+O3) predicted by both model systems using the modified     

Weekday/weekend ozone differences: what can we learn from them?

A national analysis of weekday/weekend ozone (O3) differences demonstrates significant variation across the country. Weekend 1-hr or 8-hr maximum O3 varies from 15% lower than weekday levels to 30% higher. The weekend O3 increases are primarily found in and around large coastal cities in California and large cities in the Midwest and Northeast Corridor. Both the average and the 95th percentile of the daily 1-hr and 8-hr maxima exhibit the same general pattern. Many sites that have elevated O3 also have higher O3 on weekends even though traffic and O3 precursor levels are substantially reduced on weekends. Detailed studies of this phenomenon indicate that the primary cause of the higher O3 on weekends is the reduction in oxides of nitrogen (NOx) emissions on weekends in a volatile organic compound (VOC)-limited chemical regime. In contrast, the lower O3 on weekends in other locations is probably a result of NOx reductions in a NOx-limited regime. The NOx reduction explanation is supported by a wide range of ambient analyses and several photochemical modeling studies. Changes in the timing and location of emissions and meteorological factors play smaller roles in weekend O3 behavior. Weekday/weekend temperature differences do not explain the weekend effect but may modify it.     

Determination of volatile organic profiles and photochemical potentials from chemical manufacture process vents

The main objective of this study was to monitor the volatile organic compounds (VOCs) in the stack gas released from organic chemical industrial plants to determine emission factors. Samples from 52 stacks, with or without air pollution control devices (APCDs), from seven industrial processes were taken and VOCs measured using U.S. Environmental Protection Agency (EPA) Method 18. These 7 processes, including 26 plants, were the manufacturers of acrylonitrile-butadiene-styrene (ABS), polyvinyl chloride (PVC), polystyrene (PS), acrylic resin (ACR), vinyl chloride (VC), para-terephthalic acid (PTA), and synthetic fiber (SYF). The results clearly indicate significant variations of emission factors among the various industrial processes, particularly emission factors for those without APCDs. As expected, those with APCDs yield much less emission factors. Regardless of those with or without APCDs, the order of manufacturing processes with regard to VOC emission factors is SYF > ABS > PS >ACR > PTA > PVC > VC. The emission factors for some processes also differ from those in EPA-42 data file. The VOC profiles further indicate that some VOCs are not listed in the U.S. VOC/Particulate Matter Speciation Data System (SPECIATE). The potential O3 formation is determined from the total amount of VOC emitted for each of seven processes. The resultant O3 yield varied from 0.22 (ACR) to 2.33 g O3 g(-1) VOC (PTA). The significance of this O3 yield is discussed.     

On the local and regional influence on ground-level ozone concentrations in Hong Kong

Hong Kong is a densely populated city situated in the fast developing Pearl River Delta of southern China. In this study, the recent data on ozone (O3) and related air pollutants obtained at three sites in Hong Kong are analyzed to show the variations of O3 in urban, sub-urban and rural areas and the possible regional influences. Highest monthly averaged O3 was found at a northeastern rural site and lowest O3 level was observed at an urban site. The levels of NOx, CO, SO2 and PM10 showed a different spatial pattern with the highest level in the urban site and lowest at the rural site. Analysis of chemical species ratios such as SO2/NOx and CO/NOx indicated that the sites were under the influences of local and regional emissions to varying extents reflecting the characteristics of emission sources surround the respective sites. Seasonal pattern of O3 is examined. Low O3 level was found in summer and elevated levels occurred in autumn and spring. The latter appears different from the previous result obtained in 1996 indicating a single maximum occurring in autumn. Principal component analysis was used to further elucidate the relationships of air pollutants at each site. As expected, the O3 variation in the northeastern rural area was largely determined by regional chemical and transport processes, while the O3 variability at the southwestern suburban and urban sites were more influenced by local emissions. Despite the large difference in O3 levels across the sites, total potential ozone (O3+NO2) showed little variability. Cases of high O3 episodes were presented and elevated O3 levels were formed under the influence of tropical cyclone bringing in conditions of intense sunlight, high temperature and light winds. Elevated O3 levels were also found to correlate with enhanced ratio of SO2 to NOx, suggesting influence of regional emissions from the adjacent Pearl River Delta region.     

The potential near-source ozone impacts of upstream oil and gas industry emissions

Increased drilling in urban areas overlying shale formations and its potential impact on human health through decreased air quality make it important to estimate the contribution of oil and gas activities to photochemical smog. Flares and compressor engines used in natural gas operations, for example, are large sources not only of NOx but also offormaldehyde, a hazardous air pollutant and powerful ozone precursor We used a neighborhood scale (200 m horizontal resolution) three-dimensional (3D) air dispersion model with an appropriate chemical mechanism to simulate ozone formation in the vicinity ofa hypothetical natural gas processing facility, based on accepted estimates of both regular and nonroutine emissions. The model predicts that, under average midday conditions in June, regular emissions mostly associated with compressor engines may increase ambient ozone in the Barnett Shale by more than 3 ppb beginning at about 2 km downwind of the facility, assuming there are no other major sources of ozone precursors. Flare volumes of 100,000 cubic meters per hour ofnatural gas over a period of 2 hr can also add over 3 ppb to peak 1-hr ozone somewhatfurther (>8 km) downwind, once dilution overcomes ozone titration and inhibition by large flare emissions of NOx. The additional peak ozone from the hypothetical flare can briefly exceed 10 ppb about 16 km downwind. The enhancements of ambient ozone predicted by the model are significant, given that ozone control strategy widths are of the order of a few parts per billion. Degrading the horizontal resolution of the model to 1 km spuriously enhances the simulated ozone increases by reducing the effectiveness of ozone inhibition and titration due to artificial plume dilution.     

Bioethanol-gasoline fuel blends: exhaust emissions and morphological characterization of particulate from a moped engine

This study was aimed at evaluating the effects of gasoline-ethanol blends on the exhaust emissions in a catalyst-equipped four-stroke moped engine. The ethanol was blended with unleaded gasoline in at percentages (10, 15, and 20% v/v). The regulated pollutants and the particulate matter emissions were evaluated over the European ECE R47 driving cycle on the chassis dynamometer bench. Particulate matter was characterized in terms of total mass collected on filters and total number ofparticles in the range 7 nm-10 microm measured by electrical low-pressure impactor (ELPI). In addition, particle-phase polycyclic aromatic hydrocarbons (PAHs) emissions were evaluated to assess the health impact of the emitted particulate. Finally, an accurate morphological analysis was performed on the particulate by high-resolution transmission electron microscope (TEM) equipped with a digital image-processing/data-acquisition system. In general, CO emission reductions of 60-70% were obtained with 15 and 20% v/v ethanol blends, while the ethanol use did not reduce hydrocarbon (HC) and NOx emissions. No evident effect of ethanol on the particulate mass emissions and associated PAHs emissions was observed. Twenty-one PAHs were quantified in the particulate phase with emissions ranging from 26 to 35 microg/km and benzo[a]pyrene equivalent (BaPeq) emission factors from 2.2 to 4.1 microg/km. Both particulate matter and associated PAHs with higher carcinogenic risk were mainly emitted in the submicrometer size range (<0.1 microm). On the basis of the TEM observations, no relevant effect of the ethanol use on the particulate morphology was evidenced, showing aggregates composed ofprimary particles with mean diameters in the range 17.5-32.5 nm.     

Characterization of hydrocarbons, halocarbons and carbonyls in the atmosphere of Hong Kong

Ambient air quality measurements of 156 species including 39 alkanes, 32 alkenes, 2 alkynes, 24 aromatic hydrocarbons, 43 halocarbons and 16 carbonyls, were carried out for 120 air samples collected at two sampling stations (CW and TW) in 2001 throughout Hong Kong. Spatial variations of volatile organic compounds (VOCs) in the atmosphere were investigated. Levels of most alkanes and alkenes at TW site were higher than that at the CW site, while the BTEX concentrations at the two sites were close. The BTEX ratios at CW and TW were 1.6:10.1:1.0:1.6 and 2.1:10.8:1.0:2.0, respectively. For major halogenated hydrocarbons, the mean concentrations of chloromethane, CFCs 12 and 22 did not show spatial variations at the two sites. However, site-specific differences were observed for trichloroethene and tetrachloroethene. Furthermore, there were no significant differences for carbonyls such as formaldehyde, acetaldehyde and acetone between the two sites. The levels of selected hydrocarbons in winter were 1-5 times that in summer. There were no common seasonal trends for carbonyls in Hong Kong. The ambient level of formaldehyde, the most abundant carbonyl, was higher in summer. However, levels of acetaldehyde, acetone and benzaldehyde in winter were 1.6-3.8 times that in summer. The levels of CFCs 11 and 12, and chloromethane in summer were higher than that in winter. Strong correlation of most hydrocarbons with propene and n-butane suggested that the primary contributors of hydrocarbons were vehicular emissions in Hong Kong. In addition, gasoline evaporation, use of solvents, leakage of liquefied petroleum gas (LPG), natural gas leakage and other industrial emissions, and even biogenic emissions affected the ambient levels of hydrocarbons. The sources of halocarbons were mainly materials used in industrial processes and as solvents. Correlation analysis suggested that photochemical reactions made significant contributions to the ambient levels of carbonyls in summer whereas in winter motor vehicle emissions would be the major sources of the carbonyls. The photochemical reactivity of selected VOCs was estimated in this study. The largest contributors to ozone formation were formaldehyde, toluene, propene, m,p-xylene, acetaldehyde, 1-butene/i-butene, isoprene and n-butane, suggesting that motor vehicles, gasoline evaporation, use of solvents, leakage of LPG, photochemical processes and biogenic emission are sources in the production of ozone. On the other hand, VOCs from vehicles and gasoline evaporation were predominant with respect to reactions with OH radical.