Vertical and diurnal characterization of volatile organic compounds in ambient air in urban areas

More than half of the world's population lives in cities, and their populations are rapidly increasing. Information on vertical and diurnal characterizations of volatile organic compounds (VOCs) in urban areas with heavy ambient air pollution can help further understand the impact of ambient VOCs on the local urban environment. This study characterized vertical and diurnal variations in VOCs at 2, 13, 32, 58, and 111 m during four daily time periods (7:00 to 9:00 a.m., 12:00 to 2:00 p.m., 5:00 to 7:00 p.m., and 11:00 p.m. to 1:00 a.m.) at the upwind of a high-rise building in downtown, Kaohsiung City, Taiwan. The study used gas chromatography-mass spectrometry to analyze air samples collected by silica-coated canisters. The vertical distributions of ambient VOC profiles showed that VOCs tended to decrease at greater heights. However, VOC levels were found to be higher at 13 m than at ground level at midnight from 11:00 p.m. to 1:00 a.m. and higher at 32 than 13 m between 7:00 and 9:00 a.m. These observations suggest that vertical dispersion and dilution of airborne pollutants could be jointly affected by local meteorological conditions and the proximity of pollution sources. The maximum concentration of VOCs was recorded during the morning rush hours from 7:00 to 9:00 a.m., followed by rush hours from 5:00 to 7:00 p.m., hours from 12:00 to 2:00 p.m., and hours from 11:00 p.m. to 1:00 a.m., indicating that the most VOC compounds in urban air originate from traffic and transportation emissions. The benzene-toluene-ethyl benzene-xylene (BTEX) source analysis shows that BTEX at all heights were mostly associated with vehicle transportation activities on the ground.     

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.     

Volatile organic compounds in the air of Izmir,Turkey

A sampling program was conducted to determine the ambient VOC levels in the city of Izmir, Turkey during daytime and overnight periods between mid-August and mid-September 1998. Sampling sites were selected at high-density traffic roads and junctions far from stationary VOC sources. Samples were analyzed for benzene, toluene, m, p-xylene and o-xylene (BTX), alkylbenzenes (ethylbenzene, 1,3,5-trimethylbenzene, 1,2,4-trimethylbenzene), n-hexane and, n-heptane. Results were compared with similar data from other cities around the world and for probable health dangers and sources of the compounds. Results of this study indicated that Izmir has rather high ambient BTX concentrations compared to many polluted cities in the world. Toluene was the most abundant VOC in Izmir air and was followed by xylenes, benzene and alkylbenzenes, respectively. All were strongly dependent on the expected daily variations of traffic flow in the city. The concentrations of other VOCs correlated well with benzene concentration at most sampling sites, excluding Gumuldur station indicating that ambient VOC levels were mainly affected by motor vehicle emissions. The toluene-to-benzene ratios for urban and non-urban sites were in good agreement with previously reported values, indicating a good relationship between the motor vehicle emissions and ambient VOC levels.     

VOC source identification from personal and residential indoor,outdoor and workplace microenvironment samples in EXPOLIS-Helsinki,Finland

Principal component analyses (varimax rotation) were used to identify common sources of 30 target volatile organic compounds (VOCs) in residential outdoor, residential indoor and workplace microenvironment and personal 48-h exposure samples, as a component of the EXPOLIS-Helsinki study. Variability in VOC concentrations in residential outdoor microenvironments was dominated by compounds associated with long-range transport of pollutants, followed by traffic emissions, emissions from trees and product emissions. Variability in VOC concentrations in environmental tobacco smoke (ETS) free residential indoor environments was dominated by compounds associated with indoor cleaning products, followed by compounds associated with traffic emissions, long-range transport of pollutants and product emissions. Median indoor/outdoor ratios for compounds typically associated with traffic emissions and long-range transport of pollutants exceeded 1, in some cases quite considerably, indicating substantial indoor source contributions. Changes in the median indoor/outdoor ratios during different seasons reflected different seasonal ventilation patterns as increased ventilation led to dilution of those VOC compounds in the indoor environment that had indoor sources. Variability in workplace VOC concentrations was dominated by compounds associated with traffic emissions followed by product emissions, long-range transport and air fresheners. Variability in VOC concentrations in ETS free personal exposure samples was dominated by compounds associated with traffic emissions, followed by long-range transport, cleaning products and product emissions. VOC sources in personal exposure samples reflected the times spent in different microenvironments, and personal exposure samples were not adequately represented by any one microenvironment, demonstrating the need for personal exposure sampling.     

Modeling an air pollution episode in northwestern United States: Identifying the effect of nitrogen oxide and volatile organic compound emission changes on air pollutants formation using direct sensitivity analysis

Air quality impacts of volatile organic compound (VOC) and nitrogen oxide (NO_x) emissions from major sources over the northwestern United States are simulated. The comprehensive nested modeling system comprises three models: Community Multiscale Air Quality (CMAQ), Weather Research and Forecasting (WRF), and Sparse Matrix Operator Kernel Emissions (SMOKE). In addition, the decoupled direct method in three dimensions (DDM-3D) is used to determine the sensitivities of pollutant concentrations to changes in precursor emissions during a severe smog episode in July of 2006. The average simulated 8-hr daily maximum O₃ concentration is 48.9 ppb, with 1-hr O₃ maxima up to 106 ppb (40 km southeast of Seattle). The average simulated PM_2.5 (particulate matter with an aerodynamic diameter <2.5 μm) concentration at the measurement sites is 9.06 μg m^?3, which is in good agreement with the observed concentration (8.06 μg m^?3). In urban areas (i.e., Seattle, Vancouver, etc.), the model predicts that, on average, a reduction of NO_x emissions is simulated to lead to an increase in average 8-hr daily maximum O₃ concentrations, and will be most prominent in Seattle (where the greatest sensitivity is??0.2 ppb per % change of mobile sources). On the other hand, decreasing NO_x emissions is simulated to decrease the 8-hr maximum O₃ concentrations in remote and forested areas. Decreased NO_x emissions are simulated to slightly increase PM_2.5 in major urban areas. In urban areas, a decrease in VOC emissions will result in a decrease of 8-hr maximum O₃ concentrations. The impact of decreased VOC emissions from biogenic, mobile, nonroad, and area sources on average 8-hr daily maximum O₃ concentrations is up to 0.05 ppb decrease per % of emission change, each. Decreased emissions of VOCs decrease average PM_2.5 concentrations in the entire modeling domain. In major cities, PM_2.5 concentrations are more sensitive to emissions of VOCs from biogenic sources than other sources of VOCs. These results can be used to interpret the effectiveness of VOC or NO_x controls over pollutant concentrations, especially for localities that may exceed National Ambient Air Quality Standards (NAAQS).

Implications: The effect of NO_x and VOC controls on ozone and PM_2.5 concentrations in the northwestern United States is examined using the decoupled direct method in three dimensions (DDM-3D) in a state-of-the-art three-dimensional chemical transport model (CMAQ). NO_x controls are predicted to increase PM_2.5 and ozone in major urban areas and decrease ozone in more remote and forested areas. VOC reductions are helpful in reducing ozone and PM_2.5 concentrations in urban areas. Biogenic VOC sources have the largest impact on O₃ and PM_2.5 concentrations.     

Flux measurements of volatile organic compounds by the relaxed eddy accumulation method combined with a GC-FID system in urban Houston,Texas

A tall tower flux measurement setup was established in metropolitan Houston, Texas, to measure trace gas fluxes from emission sources in the urban surface layer. We describe a new relaxed eddy accumulation (REA) system combined with a dual-channel GC-FID used for VOC flux measurements, focusing on benzene, toluene, ethylbenzene and xylenes (BTEX) results. Ambient air sampled from 60 m above the ground next to a sonic anemometer was subsampled by a membrane pump and pushed into an REA valve system with two Teflon bag reservoirs, then transferred to two preconcentration units for thermal desorption. We discuss the performance of our system and the selected BTEX measurement results using approximately 8 weeks of data (May 22–July 22, 2008), presenting diurnal variations of concentrations and fluxes of these traffic tracers. The measured values exhibited diurnal cycles with dominant morning and midday peaks during weekdays related to rush hour traffic and additional weekday daytime toluene and xylenes emissions. Local evaporative emissions, likely from solvent usage, significantly contributed to the measured fluxes. We upscaled measured emissions to the county level using a high resolution land cover data set and compared the results with EPA’s National Emission Inventory (NEI).     

Impact of emissions from natural gas production facilities on ambient air quality in the Barnett Shale area: A pilot study

Rapid and extensive development of shale gas resources in the Barnett Shale region of Texas in recent years has created concerns about potential environmental impacts on water and air quality. The purpose of this study was to provide a better understanding of the potential contributions of emissions from gas production operations to population exposure to air toxics in the Barnett Shale region. This goal was approached using a combination of chemical characterization of the volatile organic compound (VOC) emissions from active wells, saturation monitoring for gaseous and particulate pollutants in a residential community located near active gas/oil extraction and processing facilities, source apportionment of VOCs measured in the community using the Chemical Mass Balance (CMB) receptor model, and direct measurements of the pollutant gradient downwind of a gas well with high VOC emissions. Overall, the study results indicate that air quality impacts due to individual gas wells and compressor stations are not likely to be discernible beyond a distance of approximately 100 m in the downwind direction. However, source apportionment results indicate a significant contribution to regional VOCs from gas production sources, particularly for lower-molecular-weight alkanes (<C6). Although measured ambient VOC concentrations were well below health-based safe exposure levels, the existence of urban-level mean concentrations of benzene and other mobile source air toxics combined with soot to total carbon ratios that were high for an area with little residential or commercial development may be indicative of the impact of increased heavy-duty vehicle traffic related to gas production

ImplicationsRapid and extensive development of shale gas resources in recent years has created concerns about potential environmental impacts on water and air quality. This study focused on directly measuring the ambient air pollutant levels occurring at residential properties located near natural gas extraction and processing facilities, and estimating the relative contributions from gas production and motor vehicle emissions to ambient VOC concentrations. Although only a small-scale case study, the results may be useful for guidance in planning future ambient air quality studies and human exposure estimates in areas of intensive shale gas production.     

Volatile organic compounds (VOCs) in urban atmosphere of Hong Kong

The assessment of volatile organic compounds (VOCs) has become a major issue of air quality network monitoring in Hong Kong. This study is aimed to identify, quantify and characterize volatile organic compounds (VOCs) in different urban areas in Hong Kong. The spatial distribution, temporal variation as well as correlations of VOCs at five roadside sampling sites were discussed. Twelve VOCs were routinely detected in urban areas (Mong Kok, Kwai Chung, Yuen Long and Causeway Bay). The concentrations of VOCs ranged from undetectable to 1396 microg/m3. Among all of the VOC species, toluene has the highest concentration. Benzene, toluene, ethylbenzene and xylenes (BTEX) were the major constituents (more than 60% in composition of total VOC detected), mainly contributed from mobile sources. Similar to other Asian cities, the VOC levels measured in urban areas in Hong Kong were affected both by automobile exhaust and industrial emissions. High toluene to benzene ratios (average T/B ratio = 5) was also found in Hong Kong as in other Asian cities. In general, VOC concentrations in the winter were higher than those measured in the summer (winter to summer ratio > 1). As toluene and benzene were the major pollutants from vehicle exhausts, there is a necessity to tighten automobile emission standards in Hong Kong.     

VOC in an urban and industrial harbor on the French North Sea coast during two contrasted meteorological situations

Two measurement campaigns of volatile organic compounds (VOC) were carried out in the industrial city of Dunkerque, using Radiello passive samplers during winter (16–23 January) and summer (6–13 June) 2007. 174 compounds were identified belonging to six chemical families. Classifying sampling sites with similar chemical profiles by hierarchical ascending classification resulted in 4 groups that reflected the influence of the main industrial and urban sources of pollution. Also, the BTEX (Benzene, Toluene, Ethylbenzene and Xylenes) quantification allowed us to map their levels of concentration. Benzene and toluene (BT) showed high concentrations in Northern Dunkerque reflecting the influence of two industrial plants. Differences among spatial distributions of the BT concentrations over contrasted meteorological conditions were also observed. An atypical ratio of T/B in the summer samples led us to investigate the BTEX origins shedding light on the contribution of pollutants transported across various zones of VOC emissions situated in Europe.     

BTEX exposures in an area impacted by industrial and mobile sources: Source attribution and impact of averaging time

The impacts of emissions plumes from major industrial sources on black carbon (BC) and BTEX (benzene, toluene, ethyl benzene, xylene isomers) exposures in communities located >10 km from the industrial source areas were identified with a combination of stationary measurements, source identification using positive matrix factorization (PMF), and dispersion modeling. The industrial emissions create multihour plume events of BC and BTEX at the measurement sites. PMF source apportionment, along with wind patterns, indicates that the observed pollutant plumes are the result of transport of industrial emissions under conditions of low boundary layer height. PMF indicates that industrial emissions contribute >50% of outdoor exposures of BC and BTEX species at the receptor sites. Dispersion modeling of BTEX emissions from known industrial sources predicts numerous overnight plumes and overall qualitative agreement with PMF analysis, but predicts industrial impacts at the measurement sites a factor of 10 lower than PMF. Nonetheless, exposures associated with pollutant plumes occur mostly at night, when residents are expected to be home but are perhaps unaware of the elevated exposure. Averaging data samples over long times typical of public health interventions (e.g., weekly or biweekly passive sampling) misapportions the exposure, reducing the impact of industrial plumes at the expense of traffic emissions, because the longer samples cannot resolve subdaily plumes. Suggestions are made for ways for future distributed pollutant mapping or intervention studies to incorporate high time resolution tools to better understand the potential impacts of industrial plumes.

Implications: Emissions from industrial or other stationary sources can dominate air toxics exposures in communities both near the source and in downwind areas in the form of multihour plume events. Common measurement strategies that use highly aggregated samples, such as weekly or biweekly averages, are insensitive to such plume events and can lead to significant under apportionment of exposures from these sources.     

Characteristics and source apportionment of VOCs measured in Shanghai,China

Volatile organic compounds (VOCs) were measured from 2007 to 2010 at the center of Shanghai, China. Because VOCs are important precursors for ozone photochemical formation, detailed information of VOC sources needs to be investigated. The results show that the measured VOC concentrations in Shanghai are dominated by alkanes (43%) and aromatics (30%), following by halo-hydrocarbons (14%) and alkenes (6%). Based on the measured VOC concentrations, a receptor model (PMF; positive matrix factorization) coupled with the information related to VOC sources (the distribution of major industrial complex, meteorological conditions, etc.) is applied to identify the major VOC sources in Shanghai. The result shows that seven major VOC sources are identified by the PMF method, including (1) vehicle related source which contributes to 25% of the measured VOC concentrations, (2) solvent based industrial source to 17%, (3) fuel evaporation to 15%, (4) paint solvent usage to 15%, (5) steel related industrial production to 12%, (6) biomass/biofuel burning to 9%, and (7) coal burning to 7%. Furthermore, ozone formation potential related to VOC sources is calculated by the MIR (maximum incremental reactivity) technique. The most significant VOC source for ozone formation potential is solvent based industrial sources (27%), paint solvent usage (24%), vehicle related emissions (17%), steel related industrial productions (14%), fuel evaporations (9%), coal burning (6%), and biomass/biofuel burning (3%). The weekend effect on the VOC concentrations shows that VOC concentrations are generally higher in the weekdays than in the weekends at the sampling site, suggesting that traffic conditions and human activities have important impacts on the VOC emissions in Shanghai.     

Ambient levels of volatile organic compounds in the atmosphere of Greater Cairo

Ambient volatile organic compounds (VOCs) samples were collected at three locations, two in urban areas in Greater Cairo (Ramsis and Haram) and background one in rural area in Menofiya province (Kafr El-Akram), during the period of June, 2004–August, 2004. The highest concentrations of VOCs were found in Ramsis, whereas the lowest concentrations were detected in Kafr El-Akram, and the difference in mean concentrations were statistically significant (p<0.001). Among all of the measured VOCs species, the contribution of individual VOC to the total VOCs concentration were very similar in Ramsis and Haram locations, toluene was the most abundant compound followed by (m, p)-xylene. This similarity implies a similar emission sources of VOCs in both urban locations, vehicle exhausts are the dominant one. Greater Cairo has high levels of volatile aromatic hydrocarbons compared with many polluted cities in the world. The BTEX (benzene: toluene: ethylbenzene: xylenes) concentration ratios were (2.01:4.94:1:4.95), (2.03:4.91:1:4.87) and (2.31:2.98:1:2.59) in Ramsis, Haram and Kafr El-Akram, respectively. The average toluene/benzene (T/B), (m, p)-xylene/benzene ((m, p)-X/B) and o-xylene/benzene (o-X/B) concentration ratios were 2.45, 1.61and 0.85, respectively in Ramsis and 2.42, 1.61 and 0.78, respectively in Haram. The ratios in both urban locations were of the same magnitude and close to those obtained from automotive exhausts, indicating that the ambient BTEX originate mainly from motor vehicle emissions. However, the (T/B), ((m, p)-X/B) and (o-X/B) concentration ratios were 1.29, 0.71 and 0.41 in Kafr El-Akram, respectively. These ratios were lower than those found in Ramsis and Haram locations and in automotive exhaust, suggesting that the BTEX in Kafr El-Akram do not come from a local source and are exclusively results from the diffusion and dispersion of VOCs produced from the traffic density in the surrounding cities. Significant positive correlation coefficients (p<0.001) were found between the concentrations of BTEX compounds at the three sampling locations. The diurnal variation of VOCs concentrations in Ramsis location showed two daily peaks linked to traffic density.     

Dependence of home outdoor particulate mass and number concentrations on residential and traffic features in urban areas

The associations between residential outdoor and ambient particle mass, fine particle absorbance, particle number (PN) concentrations, and residential and traffic determinants were investigated in four European urban areas (Helsinki, Athens, Amsterdam, and Birmingham). A total of 152 nonsmoking participants with respiratory diseases, not exposed to occupational pollution, were included in the study, which comprised a 7-day intensive exposure monitoring period of both indoor and home outdoor particle mass and number concentrations. The same pollutants were also continuously measured at ambient fixed sites centrally located to the studied areas (fixed ambient sites). Relationships between concentrations measured directly outside the homes (residential outdoor) and at the fixed ambient sites were pollutant-specific, with substantial variations among the urban areas. Differences were more pronounced for coarse particles due to resuspension of road dust and PN, which is strongly related to traffic emissions. Less significant outdoor-to-fixed variation for particle mass was observed for Amsterdam and Birmingham, predominantly due to regional secondary aerosol. On the contrary, a strong spatial variation was observed for Athens and to a lesser extent for Helsinki. This was attributed to the overwhelming and time-varied inputs from traffic and other local sources. The location of the residence and traffic volume and distance to street and traffic light were important determinants of residential outdoor particle concentrations. On average, particle mass levels in suburban areas were less than 30% of those measured for residences located in the city center. Residences located less than 10 m from a street experienced 133% higher PN concentrations than residences located further away. Overall, the findings of this multi-city study, indicated that (1) spatial variation was larger for PN than for fine particulate matter (PM) mass and varied between the cities, (2) vehicular emissions in the residential street and location in the center of the city were significant predictors of spatial variation, and (3) the impact of traffic and location in the city was much larger for PN than for fine particle mass.     

Characterization of ambient volatile organic compounds at a landfill site in Guangzhou,South China

Ambient air monitoring was conducted at Datianshan landfill, Guangzhou, South China in 1998 to investigate the seasonal and horizontal variations of trace volatile organic compounds (VOCs). Twelve sampling points over the Datianshan landfill were selected and samples were collected simultaneously using Carbontrap(TM) adsorption tubes. Thirty eight VOCs were detected in the winter, whereas 60 were detected in the summer. The VOC levels measured in summer were alkanes, 0.5-6.5 microg/m(3); aromatics, 2.3-1667 microg/m(3); chlorinated species, 0.2-31 microg/m(3); terpines, 0.1-34 microg/m(3); carbonyl species, 0.3-5.6 microg/m(3) and naphthalene and its derivatives, 0.4-27 microg/m(3). Compared to the summer samples the VOC levels in winter were much lower (mostly 1-2 orders of magnitude lower). The aromatics are dominant VOCs in landfill air both in winter and summer. High levels of alkylbenzene and terpines such as methyl-isopropylbenzene (max 1667 microg/m(3)) and limonene (max 162 microg/m(3)) cause undesirable odor. The similar correlation coefficients of BTEX in summer and winter suggest VOCs emissions were from landfill site sources. The variation of BTEX ratio at landfill site is different from that in the urban area of Guangzhou. It shows that the ambient VOCs at landfill site were different from the urban areas.     

Dependence of Home Outdoor Particulate Mass and Number Concentrations on Residential and Traffic Features in Urban Areas

Abstract

The associations between residential outdoor and ambient particle mass, fine particle absorbance, particle number (PN) concentrations, and residential and traffic determinants were investigated in four European urban areas (Helsinki, Athens, Amsterdam, and Birmingham). A total of 152 nonsmoking participants with respiratory diseases, not exposed to occupational pollution, were included in the study, which comprised a 7-day intensive exposure monitoring period of both indoor and home outdoor particle mass and number concentrations. The same pollutants were also continuously measured at ambient fixed sites centrally located to the studied areas (fixed ambient sites). Relationships between concentrations measured directly outside the homes (residential outdoor) and at the fixed ambient sites were pollutant-specific, with substantial variations among the urban areas. Differences were more pronounced for coarse particles due to resuspension of road dust and PN, which is strongly related to traffic emissions. Less significant outdoor-to-fixed variation for particle mass was observed for Amsterdam and Birmingham, predominantly due to regional secondary aerosol. On the contrary, a strong spatial variation was observed for Athens and to a lesser extent for Helsinki. This was attributed to the overwhelming and time-varied inputs from traffic and other local sources. The location of the residence and traffic volume and distance to street and traffic light were important determinants of residential outdoor particle concentrations. On average, particle mass levels in suburban areas were less than 30% of those measured for residences located in the city center. Residences located less than 10 m from a street experienced 133% higher PN concentrations than residences located further away. Overall, the findings of this multi-city study, indicated that (1) spatial variation was larger for PN than for fine particulate matter (PM) mass and varied between the cities, (2) vehicular emissions in the residential street and location in the center of the city were significant predictors of spatial variation, and (3) the impact of traffic and location in the city was much larger for PN than for fine particle mass.     

Road traffic impact on urban water quality: a step towards integrated traffic,air and stormwater modelling

Methods for simulating air pollution due to road traffic and the associated effects on stormwater runoff quality in an urban environment are examined with particular emphasis on the integration of the various simulation models into a consistent modelling chain. To that end, the models for traffic, pollutant emissions, atmospheric dispersion and deposition, and stormwater contamination are reviewed. The present study focuses on the implementation of a modelling chain for an actual urban case study, which is the contamination of water runoff by cadmium (Cd), lead (Pb), and zinc (Zn) in the Grigny urban catchment near Paris, France. First, traffic emissions are calculated with traffic inputs using the COPERT4 methodology. Next, the atmospheric dispersion of pollutants is simulated with the Polyphemus line source model and pollutant deposition fluxes in different subcatchment areas are calculated. Finally, the SWMM water quantity and quality model is used to estimate the concentrations of pollutants in stormwater runoff. The simulation results are compared to mass flow rates and concentrations of Cd, Pb and Zn measured at the catchment outlet. The contribution of local traffic to stormwater contamination is estimated to be significant for Pb and, to a lesser extent, for Zn and Cd; however, Pb is most likely overestimated due to outdated emissions factors. The results demonstrate the importance of treating distributed traffic emissions from major roadways explicitly since the impact of these sources on concentrations in the catchment outlet is underestimated when those traffic emissions are spatially averaged over the catchment area.     

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.     

Fine particulate matter emissions inventories: comparisons of emissions estimates with observations from recent field programs

Emissions inventories of fine particulate matter (PM2.5) were compared with estimates of emissions based on data emerging from U.S. Environment Protection Agency Particulate Matter Supersites and other field programs. Six source categories for PM2.5 emissions were reviewed: on-road mobile sources, nonroad mobile sources, cooking, biomass combustion, fugitive dust, and stationary sources. Ammonia emissions from all of the source categories were also examined. Regional emissions inventories of PM in the exhaust from on-road and nonroad sources were generally consistent with ambient observations, though uncertainties in some emission factors were twice as large as the emission factors. In contrast, emissions inventories of road dust were up to an order of magnitude larger than ambient observations, and estimated brake wear and tire dust emissions were half as large as ambient observations in urban areas. Although comprehensive nationwide emissions inventories of PM2.5 from cooking sources and biomass burning are not yet available, observational data in urban areas suggest that cooking sources account for approximately 5-20% of total primary emissions (excluding dust), and biomass burning sources are highly dependent on region. Finally, relatively few observational data were available to assess the accuracy of emission estimates for stationary sources. Overall, the uncertainties in primary emissions for PM2.s are substantial. Similar uncertainties exist for ammonia emissions. Because of these uncertainties, the design of PM2.5 control strategies should be based on inventories that have been refined by a combination of bottom-up and top-down methods.     

The effect of reformulated gasoline on ambient carbon monoxide concentrations in southeastern Wisconsin

Reformulated gasoline (RFG) contains oxygen additives such as methyl tertiary butyl ether or ethanol. The additives enable vehicles to burn fuel with a higher air/fuel ratio, thereby lowering the emission of carbon monoxide (CO) and volatile organic compounds (VOCs). Because VOCs react with sunlight to form ozone (O3), the Clean Air Act requires severe O3 nonattainment areas such as southeastern Wisconsin to use RFG. On July 17, 2001, the U.S. Environmental Protection Agency (EPA) granted Milwaukee, WI, and Chicago, IL, a waiver from the VOC reduction requirement of Phase II RFG. The VOC reduction requirement was lowered from 27.4% of the 1990 baseline fuel to 25.4%. The assumption was that ethanol-blended RFG would lower summertime CO concentrations sufficiently to offset the increased VOC emissions. The waiver is estimated to increase VOC emissions by approximately 0.8%, or 0.4 t of VOC on a hot summer weekday. This study evaluates whether RFG has been effective in lowering southeastern Wisconsin ambient CO concentrations. Three years of ambient CO data before RFG was introduced were compared with the first three years of ambient CO data after RFG was introduced. This paper also evaluates how the meteorology, vehicle inspection/maintenance program, vehicle miles traveled, and stationary source emissions influence CO concentrations. The winter decrease in ambient CO concentrations was found to be statistically significant, while the summer data showed no statistically significant change, indicating that RFG is most effective lowering ambient CO concentrations in cold weather.     

Improvement of health risk factors after reduction of VOC concentrations in industrial and urban areas

After reductions of fugitive and diffuse emissions by an industrial complex, a follow-up study was performed to determine the time variability of volatile organic compounds (VOCs) and the lifetime cancer risk (LCR). Passive samplers (3 M monitors) were placed outdoors (n?=?179) and indoors (n?=?75) in industrial, urban, and control areas for 4 weeks. Twenty-five compounds including n-alkanes, cycloalkanes, aromatics, chlorinated hydrocarbons, and terpenes were determined by GC/MS. The results show a significant decrease of all VOCs, especially in the industrial area and to a lesser extent in the urban area. The median outdoor concentration of benzene in the industrial area declined compared to the former study, around 85 % and about 50 % in the urban area, which in the past was strongly influenced by industrial emissions. Other carcinogenic compounds like styrene and tetrachloroethylene were reduced to approximately 60 %. VOC concentrations in control areas remained nearly unchanged. According to the determined BTEX ratios and interspecies correlations, in contrast to the previous study, traffic was identified as the main emission source in the urban and control areas and showed an increased influence in the industrial area. The LCR, calculated for benzene, styrene, and tetrachloroethylene, shows a decrease of one order of magnitude in accordance to the decreased total VOC concentrations and is now acceptable according to values proposed by the World Health Organization.