The concentrations of ozone, nitrogen oxides, and nonmethane hydrocarbons measured near the surface in a variety of urban, suburban, rural, and remote locations are analyzed and compared in order to elucidate the relationships between ozone, its photochemical precursors, and the sources of these precursors. While a large gradient is found among remote, rural, and urban/suburban nitrogen oxide concentrations, the total hydrocarbon reactivity in all continental locations is found to be comparable. Apportionment of the observed hydrocarbon species to mobile and stationary anthropogenic sources and biogenic sources suggests that present-day emission inventories for the United States underestimate the size of mobile emissions. The analysis also suggests a significant role for biogenic hydrocarbon emissions in many urban/suburban locations and a dominant role for these sources in rural areas of the eastern United States. As one moves from remote locations to rural locations and then from rural to urban/suburban locations, ozone and nitrogen oxide concentrations tend to increase in a consistent manner while total hydrocarbon reactivity does not. hydrocarbon concentrations in four chemically distinct regimes of the atmospheric boundary layer, each having a distinct mix of anthropogenic and natural hydrocarbon and NOx emissions. These regimes are: I, the urban/suburban atmosphere, which is the regime most strongly impacted by anthropogenic emissions; II, the rural atmosphere, which is somewhat less impacted by anthropogenic emissions and more impacted by natural emissions than that of the urban atmosphere; III, the atmosphere over the remote, tropical forest which is essentially free of anthropogenic volatile organic compounds (VOC) and NOx emissions and strongly influenced by natural emissions; and IV, the remote, marine atmosphere, which is not only free of anthropogenic emissions but is also characterized by relatively small biogenic sources of VOC and NO x. Because we are most interested in the conditions that foster ozone episodes, our analysis concentrates on observations made during the daylight hours of the summer months.In the sections below we first briefly summarize the fundamentals of the photochemical smog mechanism and the nonlinearities inherent in this system and then discuss the concentrations of 03, NOx, and hydrocarbons typically observed in the four regimes listed above. PHOTOCHEMICAL SMOGWhile uncertainties remain in our understanding of tropospheric photochemistry, the basic set of reactions that lead to 03 production have been identified. These reactions, commonly referred to in the aggregate as the "photochemical smog" mechanism, involve the oxidation of hydrocarbons and other volatile organic compounds in the presence of nitrogen oxides (NOx) and sunlight [Haagen-Srnit, 1952; $einfeld, 1988]. Typical of this mechanism are reactions (R1) through (R7),RH + OH--> R + H20 (R2) R + 02 + M--> RO2 + M (R3) RO 2 + NO--> RO + NO 2 (R4) RO + 0 2 --> HO 2 + RCHO 6037

Emission samples for toxicity testing and detailed chemical characterization were collected from a variety of gasoline- and diesel-fueled in-use vehicles operated on the Unified Driving Cycle on a chassis dynamometer. Gasoline vehicles included normal particle mass (particulate matter [PM]) emitters (tested at 72 and 30 degrees F), "black" and "white" smokers, and a new-technology vehicle (tested at 72 degrees F). Diesel vehicles included current-technology vehicles (tested at 72 and 30 degrees F) and a high PM emitter. Total PM emission rates ranged from below 3 mg/mi up to more than 700 mg/mi for the white smoker gasoline vehicle. Emission rates of organic and elemental carbon (OC/EC), elements (metals and associated analytes), ions, and a variety of particulate and semi-volatile organic compounds (polycyclic aromatic hydrocarbons [PAH], nitro-PAH, oxy-PAH, hopanes, and steranes) are reported for these vehicles. Speciated organic analysis also was conducted on the fuels and lube oils obtained from these vehicles after the emissions testing. The compositions of emissions were highly dependent on the fuel type (gasoline vs. diesel), the state of vehicle maintenance (low, average, or high emitters; white or black smokers), and ambient conditions (i.e., temperature) of the vehicles. Fuel and oil analyses from these vehicles showed that oil served as a repository for combustion byproducts (e.g., PAH), and oil-burning gasoline vehicles emitted PAH in higher concentrations than did other vehicles. These PAH emissions matched the PAH compositions observed in oil.

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A study to characterize particulate matter emissions from 195 in-use gasoline and diesel passenger vehicles was conducted during the summer of 1996 and the winter of 1997 in the Denver, Colorado region. Vehicles were tested as received on chassis dynamometers using the Federal Test Procedure (FTP) Urban Dynamometer Driving Schedule (UDDS). Both PM-10 and regulated emissions were measured for each phase of the UDDS. Approximately 88% of the PM-10 collected was carbonaceous material, of which the average organic fraction was 0.7 for gasoline vehicles and 0.4 for diesel vehicles. This suggests that the organic carbon (OC) to elemental carbon (EC) split may be useful in separating light-duty gasoline from diesel PM emissions. Sulfate emission rates averaged 0.45 and 3.51 mg/mi for gasoline and diesel vehicles, indicating that the EPA's mobile emissions model overpredicts sulfate emission rates. Elements identified by X-ray fluorescence averaged between 3 and 9% of the PM-10 mass. Polynuclear aromatic hydrocarbon (PAH) profiles developed may help distinguish between gasoline and diesel vehicles in source apportionment studies. Total PAH emissions, however, were not a good candidate as a tracer of gasoline PM emissions. Hopane and sterane emissions were very similar across the fleet and may be useful tracers for mobile source PM emissions. Overall, emission rates varied significantly with vehicle classification and driving condition, suggesting that a single profile representing the entire fleet will need to carefully reflect the local fleet composition and the local weighting of cold, hot, and hot-stabilized emissions.

Since the mid-1970s, ozone (O3) levels in portions of California's South Coast Air Basin (SoCAB) on weekends have been as high as or higher than levels on weekdays, even though emissions of O3 precursors are lower on weekends. Analysis of the ambient data indicates that the intensity and spatial extent of the weekend O3 effect are correlated with-day-of-week variations in the extent of O3 inhibition caused by titration with nitric oxide (NO), reaction of hydroxyl radical (OH) with nitrogen dioxide (NO2), and rates of O3 accumulation. Lower NO mixing ratios and higher NO2/oxides of nitrogen (NOx) ratios on weekend mornings allow O3 to begin accumulating approximately an hour earlier on weekends. The weekday/weekend differences in the duration of O3 accumulation remained relatively constant from 1981 to 2000. In contrast, the rate of O3 accumulation decreased by one-third to one-half over the same period; the largest reductions occurred in the central basin on weekdays. Trends in mixing ratios of O3 precursors show a transition to lower volatile organic compound (VOC)/NOx ratios caused by greater reductions in VOC emissions. Reductions in VOC/NOx ratios were greater on weekdays, resulting in higher VOC/NOx ratios on weekends relative to weekdays. Trends in VOC/NOx ratios parallel the downward trend in peak O3 levels, a shift in the location of peak O3 from the central to the eastern portion of the basin, and an increase in the magnitude and spatial extent of the weekend O3 effect.

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As part of the Gasoline/Diesel PM Split Study, relatively large fleets of gasoline vehicles 53 and diesel vehicles 34 were tested on a chassis dynamometer to develop chemical source profiles for source attribution of atmospheric particulate matter in California's South Coast Air Basin. Gasoline vehicles were tested in cold-start and warm-start conditions, and diesel vehicles were tested through several driving cycles. Tailpipe emissions of particulate matter were analyzed for organic tracer compounds, including hopanes, steranes, and polycyclic aromatic hydrocarbons. Large intervehicle variation was seen in emission rate and composition, and results were averaged to examine the impacts of vehicle ages, weight classes, and driving cycles on the variation. Average profiles, weighted by mass emission rate, had much lower uncertainty than that associated with intervehicle variation. Mass emission rates and elemental carbon/organic carbon (EC/OC) ratios for gasoline vehicle age classes were influenced most by use of cold-start or warm-start driving cycle (factor of 2-7). Individual smoker vehicles had a large range of mass and EC/OC (factors of 40 and 625, respectively). Gasoline vehicle age averages, data on vehicle ages and miles traveled in the area, and several assumptions about smoker contributions were used to create emissions profiles representative of on-road vehicle fleets in the Los Angeles area in 2001. In the representative gasoline fleet profiles, variation was further reduced, with coldstart or warm-start and the representation of smoker vehicles making a difference of approximately a factor of two in mass emission rate and EC/OC. Diesel vehicle profiles were created on the basis of vehicle age, weight class, and driving cycle. Mass emission rate and EC/OC for diesel averages were influenced by vehicle age (factor of 2-5), weight class (factor of 2-7), and driving cycle (factor of 10 -20). Absolute and relative emissions of molecular marker compounds showed levels of variation similar to those of mass and EC/OC.

The chemical mass balance (CMB) receptor model was applied to the chemically speciated diurnal particulate matter samples acquired at nine locations in California's South Coast Air Basin (SOCAB) during the summer and fall of 1987 as part of the Southern California Air Quality Study (SCAQS). Source profiles applicable to the Los Angeles area were used to apportion PM,, and PM,, (particles with aerodynamic diameters < 2.5 and 10 pm, respectively) to primary paved road dust, primary construction dust, primary motor vehicle exhaust, primary marine aerosol, secondary ammonium