Past and future ozone trends in California's South Coast Air Basin: reconciliation of ambient measurements with past and projected emission inventories.

UNLABELLED: This paper updates the historic trends (1980-2010) in ambient ozone and ozone precursor concentrations in the South Coast Air Basin (SoCAB) and examines the evolution of the ozone-precursor relationship in the Basin. Whereas reductions in NOx (oxide of nitrogen) emissions have decreased nitrate and PM2.5 (particulate matter with an aerodynamic diameter < or = 2.5 microm) concentrations in the Basin during the past decade, ozone levels have increased at the central basin locations since about 2005 following a reversal in the decline of volatile organic compound (VOC)/NOx ratios during the previous two decades. A chemical box model was used to simulate the effects of changes in precursor concentrations on ozone formation using day-of-week-specific initial precursor concentrations that were derived from measurements and'projected to 2020 based on expected emission reductions from 2005 (-10% VOC and -50% NOx). Results show that peak ozone formation rates in 2020 will increase on weekdays by a factor of 3 relative to 2005 and will be comparable to 1995 weekday and 2005 Sunday rates. Ozone production will become precursor limited on Sundays in 2020, but with higher initial rates than 2005. Although a greater NOx reduction scenario in 2020 of -75% will result in even higher initial ozone formation rates, precursor limitation is reached quickly, leading to a further shift westward in the location of peak ozone levels. However ozone levels will likely be lower in downwind areas where transport is more important than local production of ozone. The ambient versus emission inventory reconciliation indicates a factor of 2 underestimation of VOC emissions in 2009 relative to NOx. Other analyses suggest that there is an overall increase in VOC emissions on hot days that is not fully accounted for by emission inventory estimates. Air quality models using emission inventories that underestimate VOC emissions relative to NOx may lead to inaccurate forecasting of the consequence of emission reductions. IMPLICATIONS: The rate and efficiency of ozone formation and accumulation in the SoCAB is more rapid than would be indicated by air quality model simulations based on the current inventory. Projected reductions in NOx emissions without concurrent reductions in VOC emissions will likely cause ozone to increase during the next decade within central regions of the SoCAB compared with a flat or slightly declining trend in far downwind locations. Air quality statistics that are commonly used to track progress toward attainment, such as basin-wide ozone design value and standard exceedances mask these varying trends within the Basin.

Multispecies remote sensing measurements of vehicle emissions on Sherman Way in Van Nuys, California.

UNLABELLED: As part of the 2010 Van Nuys tunnel study, researchers from the University of Denver measured on-road fuel-specific light-duty vehicle emissions from nearly 13,000 vehicles on Sherman Way (0.4 miles west of the tunnel) in Van Nuys, California, with its multispecies Fuel Efficiency Automobile Test (FEAT) remote sensor a week ahead of the tunnel measurements. The remote sensing mean gram per kilogram carbon monoxide (CO), hydrocarbon (HC), and oxide of nitrogen (NO(x)) measurements are 8.9% lower 41% higher, and 24% higher than the tunnel measurements, respectively. The remote sensing CGO/NO(x) and HC/NO(x) mass ratios are 28% lower and 20% higher than the comparable tunnel ratios. Comparisons with the historical tunnel measurements show large reductions in CO, HC, and NO(x) over the past 23 yr, but little change in the HC/NO(x) mass ratio since 1995. The fleet CO and HC emissions are increasingly dominated by a few gross emitters, with more than a third of the total emissions being contributed by less than 1% of the fleet. An example of this is a 1995 vehicle measured three times with an average HC emission of 419 g/kg fuel (two-stroke snowmobiles average 475 g/kg fuel), responsible for 4% of the total HC emissions. The 2008 economic downturn dramatically reduced the number of new vehicles entering the fleet, leading to an age increase (> 1 model year) of the Sherman Way fleet that has increased the fleet's ammonia (NH3) emissions. The mean NH3 levels appear little changed from previous measurements collected in the Van Nuys tunnel in 1993. Comparisons between weekday and weekend data show few fleet differences, although the fraction of light-duty diesel vehicles decreased from the weekday (1.7%) to Saturday (1.2%) and Sunday (0.6%). IMPLICATIONS: On-road remote sensing emission measurements of light-duty vehicles on Sherman Way in Van Nuys, California, show large historical emission reductions for CO and HC emissions despite an older fleet arising from the 2008 economic downturn. Fleet CO and HC emissions are increasingly dominated by a few gross emitters, with a single 1995 vehicle measured being responsible for 4% of the entire fleet's HC emissions. Finding and repairing and/or scrapping as little as 2% of the fleet would reduce on-road tailpipe emissions by as much as 50%. Ammonia emissions have locally increased with the increasing fleet age.

Comparison of the MOVES2010a, MOBILE6.2, and EMFAC2007 mobile source emission models with on-road traffic tunnel and remote sensing measurements.

UNLABELLED: The Desert Research Institute conducted an on-road mobile source emission study at a traffic tunnel in Van Nuys, California, in August 2010 to measure fleet-averaged, fuel-based emission factors. The study also included remote sensing device (RSD) measurements by the University of Denver of 13,000 vehicles near the tunnel. The tunnel and RSD fleet-averaged emission factors were compared in blind fashion with the corresponding modeled factors calculated by ENVIRON International Corporation using U.S. Environmental Protection Agency's (EPA's) MOVES2010a (Motor Vehicle Emissions Simulator) and MOBILE6.2 mobile source emission models, and California Air Resources Board's (CARB's) EMFAC2007 (EMission FACtors) emission model. With some exceptions, the fleet-averaged tunnel, RSD, and modeled carbon monoxide (CO) and oxide of nitrogen (NO(x)) emission factors were in reasonable agreement (+/- 25%). The nonmethane hydrocarbon (NMHC) emission factors (specifically the running evaporative emissions) predicted by MOVES were insensitive to ambient temperature as compared with the tunnel measurements and the MOBILE- and EMFAC-predicted emission factors, resulting in underestimation of the measured NMHC/NO(x) ratios at higher ambient temperatures. Although predicted NMHC/NO(x) ratios are in good agreement with the measured ratios during cooler sampling periods, the measured NMHC/NO(x) ratios are 3.1, 1.7, and 1.4 times higher than those predicted by the MOVES, MOBILE, and EMFAC models, respectively, during high-temperature periods. Although the MOVES NO(x) emission factors were generally higher than the measured factors, most differences were not significant considering the variations in the modeled factors using alternative vehicle operating cycles to represent the driving conditions in the tunnel. The three models predicted large differences in NO(x) and particle emissions and in the relative contributions of diesel and gasoline vehicles to total NO(x) and particulate carbon (TC) emissions in the tunnel. IMPLICATIONS: Although advances have been made to mobile source emission models over the past two decades, the evidence that mobile source emissions of carbon monoxide and hydrocarbons in urban areas were underestimated by as much as a factor of 2-3 in past inventories underscores the need for on-going verification of emission inventories. Results suggest that there is an overall increase in motor vehicle NMHC emissions on hot days that is not fully accounted for by the emission models. Hot temperatures and concomitant higher ratios of NMHC emissions relative to NO(x) both contribute to more rapid and efficient formation of ozone. Also, the ability of EPA's MOVES model to simulate varying vehicle operating modes places increased importance on the choice of operatingmodes to evaluate project-level emissions.

Emission changes resulting from the San Pedro Bay, California Ports Truck Retirement Program.

Recent U.S. Environmental Protection Agency emissions regulations have resulted in lower emissions of particulate matter and oxides of nitrogen from heavy-duty diesel trucks. To accelerate fleet turnover the State of California in 2008 along with the Ports of Los Angeles and Long Beach (San Pedro Bay Ports) in 2006 passed regulations establishing timelines forcing the retirement of older diesel trucks. On-road emissions measurements of heavy-duty diesel trucks were collected over a three-year period, beginning in 2008, at a Port of Los Angeles location and an inland weigh station on the Riverside freeway (CA SR91). At the Port location the mean fleet age decreased from 12.7 years in April of 2008 to 2.5 years in May of 2010 with significant reductions in carbon monoxide (30%), oxides of nitrogen (48%) and infrared opacity (a measure of particulate matter, 54%). We also observed a 20-fold increase in ammonia emissions as a result of new, stoichiometrically combusted, liquefied natural gas powered trucks. These results compare with changes at our inland site where the average ages were 7.9 years in April of 2008 and 8.3 years in April of 2010, with only small reductions in oxides of nitrogen (10%) being statistically significant. Both locations have experienced significant increases in nitrogen dioxide emissions from new trucks equipped with diesel particle filters; raising the mean nitrogen dioxide to oxides of nitrogen ratios from less than 10% to more than 30% at the Riverside freeway location.

Measuring in-cabin school bus tailpipe and crankcase PM2.5: a new dual tracer method.

Exposures of occupants in school buses to on-road vehicle emissions, including emissions from the bus itself, can be substantially greater than those in outdoor settings. A dual tracer method was developed and applied to two school buses in Seattle in 2005 to quantify in-cabin fine particulate matter (PM2.5) concentrations attributable to the buses' diesel engine tailpipe (DPMtp) and crankcase vent (PMck) emissions. The new method avoids the problem of differentiating bus emissions from chemically identical emissions of other vehicles by using a fuel-based organometallic iridium tracer for engine exhaust and by adding deuterated hexatriacontane to engine oil. Source testing results showed consistent PM:tracer ratios for the primary tracer for each type of emissions. Comparisons of the PM:tracer ratios indicated that there was a small amount of unburned lubricating oil emitted from the tailpipe; however, virtually no diesel fuel combustion products were found in the crankcase emissions. For the limited testing conducted here, although PMck emission rates (averages of 0.028 and 0.099 g/km for the two buses) were lower than those from the tailpipe (0.18 and 0.14 g/km), in-cabin PMck concentrations averaging 6.8 microg/m3 were higher than DPMtp (0.91 microg/m3 average). In-cabin DPMtp and PMck concentrations were significantly higher with bus windows closed (1.4 and 12 microg/m3, respectively) as compared with open (0.44 and 1.3 microg/m3, respectively). For comparison, average closed- and open-window in-cabin total PM2.5 concentrations were 26 and 12 microg/m3, respectively. Despite the relatively short in-cabin sampling times, very high sensitivities were achieved, with detection limits of 0.002 microg/m3 for DPMtp and 0.05 microg/m3 for PMck.

Quantification of Self Pollution from Two Diesel School Buses using Three Independent Methods.

We monitored two Seattle school buses to quantify the buses' self pollution using the dual tracers (DT), lead vehicle (LV), and chemical mass balance (CMB) methods. Each bus drove along a residential route simulating stops, with windows closed or open. Particulate matter (PM) and its constituents were monitored in the bus and from a LV. We collected source samples from the tailpipe and crankcase emissions using an on-board dilution tunnel. Concentrations of PM(1), ultrafine particle counts, elemental and organic carbon (EC/OC) were higher on the bus than the LV. The DT method estimated that the tailpipe and the crankcase emissions contributed 1.1 and 6.8 mug/m(3) of PM(2.5) inside the bus, respectively, with significantly higher crankcase self pollution (SP) when windows were closed. Approximately two-thirds of in-cabin PM(2.5) originated from background sources. Using the LV approach, SP estimates from the EC and the active personal DataRAM (pDR) measurements correlated well with the DT estimates for tailpipe and crankcase emissions, respectively, although both measurements need further calibration for accurate quantification. CMB results overestimated SP from the DT method but confirmed crankcase emissions as the major SP source. We confirmed buses' SP using three independent methods and quantified crankcase emissions as the dominant contributor.

Real-World Vehicle Emissions: A Summary of the 18th Coordinating Research Council On-Road Vehicle Emissions Workshop.

The Coordinating Research Council (CRC) convened its 18th On-Road Vehicle Emissions Workshop March 31- April 2, 2008, with 104 presentations describing the most recent mobile source-related emissions research. In this paper we summarize the presentations from researchers whose efforts are improving our understanding of the contribution of mobile sources to air quality. Participants in the workshop discussed emission models and emissions inventories, results from gas- and particle-phase emissions studies from spark-ignition and diesel-powered vehicles (with an emphasis in this workshop on particle emissions), effects of fuels on emissions, evaluation of in-use emission-control programs, and efforts to improve our capabilities in performing on-board emissions measurements, as well as topics for future research.

Detailed characterization and profiles of crankcase and diesel particulate matter exhaust emissions using speciated organics.

A monitoring campaign was conducted in August-September 2005 to compare different experimental approaches quantifying school bus self-pollution. As part of this monitoring campaign, a detailed characterization of PM2.5 diesel engine emissions from the tailpipe and crankcase emissions from the road draft tubes was performed. To distinguish between tailpipe and crankcase vent emissions, a deuterated alkane, n-hexatriacontane-d74 (n-C36D74) was added to the engine oil to serve as an intentional quantitative tracer for lubricating oil PM emissions. This paper focuses on the detailed chemical speciation of crankcase and tailpipe PM emissions from two school buses used in this study. We found that organic carbon emission rates were generally higher from the crankcase than from the tailpipe for these two school buses, while elemental carbon contributed significantly only in the tailpipe emissions. The n-C36D74 that was added to the engine oil was emitted at higher rates from the crankcase than the tailpipe. Tracers of engine oil (hopanes and steranes) were present in much higher proportion in crankcase emissions. Particle-associated PAH emission rates were generally very low (< 1 microg/km), but more PAH species were present in crankcase than in tailpipe emissions. The speciation of samples collected in the bus cabins was consistent with most of the bus self-pollution originating from crankcase emissions.

Real-world vehicle emissions: a summary of the Seventeenth Coordinating Research Council On-Road Vehicle Emissions Workshop.

The Coordinating Research Council, Inc. (CRC) held its 17th On-Road Vehicle Emissions Workshop in March 2007, where results of the most recent on-road vehicle emissions research were presented. We summarize ongoing work from researchers who are engaged in improving our understanding of the role and contribution of mobile sources to ambient air quality and emission inventories. Participants in the Workshop discussed efforts to improve mobile source emission models, light- and heavy-duty vehicle emissions measurements, on- and off-road emissions measurements, effects of fuels and lubricating oils on emissions, as well as emerging issues and topics for future research.

Differences between weekday and weekend air pollutant levels in Atlanta; Baltimore; Chicago; Dallas-Fort Worth; Denver; Houston; New York; Phoenix; Washington, DC; and surrounding areas.

We evaluated day-of-week differences in mean concentrations of ozone (O3) precursors (nitric oxide [NO], nitrogen oxides [NOx], carbon monoxide [CO], and volatile organic compounds [VOCs]) at monitoring sites in 23 states comprising seven geographic focus areas over the period 1998-2003. Data for VOC measurements were available for six metropolitan areas in five regions. We used Wednesdays to represent weekdays and Sundays to represent weekends; we also analyzed Saturdays. At many sites, NO, NOx, and CO mean concentrations decreased at all individual hours from 6:00 a.m. to 3:00 p.m. on Sundays compared with corresponding Wednesday means. Statistically significant (p < 0.01) weekend decreases in ambient concentrations were observed for 92% of NOx, sites, 89% of CO sites, and 23% of VOC sites. Nine-hour (6:00 a.m. to 3:00 p.m.) mean concentrations of NO, NOx, CO, and VOCs declined by 65, 49, 28, and 19%, respectively, from Wednesdays to Sundays (median site responses). Despite the large reductions in ambient NOx and moderate reductions in ambient CO and VOC concentrations on weekends, ozone and particulate matter (PM) nitrate did not exhibit large changes from weekdays to weekends. The median differences between Wednesday and Sunday mean ozone concentrations at all monitoring sites ranged from 3% higher on Sundays for peak 8-hr concentrations determined from all monitoring days to 3.8% lower on Sundays for peak 1-hr concentrations on extreme-ozone days. Eighty-three percent of the sites did not show statistically significant differences between Wednesday and weekend mean concentrations of peak ozone. Statistically significant weekend ozone decreases occurred at 6% of the sites and significant increases occurred at 11% of the sites. Average PM nitrate concentrations were 2.6% lower on Sundays than on Wednesdays. Statistically significant Sunday PM nitrate decreases occurred at one site and significant increases occurred at seven sites.

Development of molecular marker source profiles for emissions from on-road gasoline and diesel vehicle fleets.

As part of the Gasoline/Diesel PM Split Study, relatively large fleets of gasoline vehicles and diesel vehicles 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 cold-start 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.

Variations in speciated emissions from spark-ignition and compression-ignition motor vehicles in California's south coast air basin.

The U.S. Department of Energy Gasoline/Diesel PM Split Study examined the sources of uncertainties in using an organic compound-based chemical mass balance receptor model to quantify the contributions of spark-ignition (SI) and compression-ignition (CI) engine exhaust to ambient fine particulate matter (PM2.5). This paper presents the chemical composition profiles of SI and CI engine exhaust from the vehicle-testing portion of the study. Chemical analysis of source samples consisted of gravimetric mass, elements, ions, organic carbon (OC), and elemental carbon (EC) by the Interagency Monitoring of Protected Visual Environments (IMPROVE) and Speciation Trends Network (STN) thermal/optical methods, polycyclic aromatic hydrocarbons (PAHs), hopanes, steranes, alkanes, and polar organic compounds. More than half of the mass of carbonaceous particles emitted by heavy-duty diesel trucks was EC (IMPROVE) and emissions from SI vehicles contained predominantly OC. Although total carbon (TC) by the IMPROVE and STN protocols agreed well for all of the samples, the STN/IMPROVE ratios for EC from SI exhaust decreased with decreasing sample loading. SI vehicles, whether low or high emitters, emitted greater amounts of high-molecular-weight particulate PAHs (benzo[ghi]perylene, indeno[1,2,3-cd]pyrene, and coronene) than did CI vehicles. Diesel emissions contained higher abundances of two- to four-ring semivolatile PAHs. Diacids were emitted by CI vehicles but are also prevalent in secondary organic aerosols, so they cannot be considered unique tracers. Hopanes and steranes were present in lubricating oil with similar composition for both gasoline and diesel vehicles and were negligible in gasoline or diesel fuels. CI vehicles emitted greater total amounts of hopanes and steranes on a mass per mile basis, but abundances were comparable to SI exhaust normalized to TC emissions within measurement uncertainty. The combustion-produced high-molecular-weight PAHs were found in used gasoline motor oil but not in fresh oil and are negligible in used diesel engine oil. The contributions of lubrication oils to abundances of these PAHs in the exhaust were large in some cases and were variable with the age and consumption rate of the oil. These factors contributed to the observed variations in their abundances to total carbon or PM2.5 among the SI composition profiles.

Real-world vehicle emissions: a summary of the Sixteenth Coordinating Research Council On-Road Vehicle Emissions Workshop.

The Coordinating Research Council held its 16th workshop in March 2006, with 83 presentations describing the most recent mobile source-related emissions research. In this paper, we summarize the presentations from researchers who are engaged in improving our understanding of the contribution of mobile sources to air quality. Participants in the workshop discussed evaluation of in-use emissions control programs, effects of fuels on emissions, emission models and emission inventories, results from gas- and particle-phase emissions studies from spark-ignition and diesel-powered vehicles, and efforts to improve our capabilities in performing on-board emissions measurements, as well as topics for future research.

Real-world vehicle emissions: A summary of the 15th coordinating research council on-road vehicle emissions workshop.

The Coordinating Research Council held its 15th workshop in April 2005, with nearly 90 presentations describing the most recent mobile source-related emissions research. In this paper, the authors summarize the presentations from researchers who are engaged in improving our understanding of the contribution of mobile sources to air quality. Participants in the workshop discussed emission models and emission inventories, results from gas- and particle-phase emissions studies from spark-ignition and diesel-powered vehicles (with an emphasis in this workshop on particle emissions), effects of fuels on emissions, evaluation of in-use emissions control programs, and efforts to improve our capabilities in performing on-board emissions measurements, as well as topics for future research.

Real-world vehicle emissions: a summary of the 14th coordinating research council on-road Vehicle Emissions Workshop.

The Coordinating Research Council held its 14th Vehicle Emissions Workshop in March 2004, where results of the most recent on-road vehicle emissions research were presented. We summarize ongoing work from researchers who are engaged in improving our understanding of the contribution of mobile sources to ambient air quality and emission inventories. Participants in the workshop discussed efforts to improve mobile source emission models, light- and heavy-duty vehicle emissions measurements, on- and off-road emissions measurements, effects of fuels and lubricating oils on emissions, as well as topics for future research.

Relationship between composition and toxicity of motor vehicle emission samples.

In this study we investigated the statistical relationship between particle and semivolatile organic chemical constituents in gasoline and diesel vehicle exhaust samples, and toxicity as measured by inflammation and tissue damage in rat lungs and mutagenicity in bacteria. Exhaust samples were collected from "normal" and "high-emitting" gasoline and diesel light-duty vehicles. We employed a combination of principal component analysis (PCA) and partial least-squares regression (PLS; also known as projection to latent structures) to evaluate the relationships between chemical composition of vehicle exhaust and toxicity. The PLS analysis revealed the chemical constituents covarying most strongly with toxicity and produced models predicting the relative toxicity of the samples with good accuracy. The specific nitro-polycyclic aromatic hydrocarbons important for mutagenicity were the same chemicals that have been implicated by decades of bioassay-directed fractionation. These chemicals were not related to lung toxicity, which was associated with organic carbon and select organic compounds that are present in lubricating oil. The results demonstrate the utility of the PCA/PLS approach for evaluating composition-response relationships in complex mixture exposures and also provide a starting point for confirming causality and determining the mechanisms of the lung effects.

Emission rates and comparative chemical composition from selected in-use diesel and gasoline-fueled vehicles.

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.

Real-world vehicle emissions: a summary of the Thirteenth Coordinating Research Council On-Road Vehicle Emissions Workshop.

The Coordinating Research Council held its thirteenth Vehicle Emissions Workshop in April 2003, when results of the most recent on-road vehicle emissions research were presented. Ongoing work from researchers who are engaged in improving understanding of the contribution of mobile sources to ambient air quality and emission inventories is summarized here. Participants in the workshop discussed efforts to improve mobile source emission models, the role of on-board diagnostic systems in inspection and maintenance programs, light- and heavy-duty vehicle emissions measurements, on- and off-road emissions measurements, effects of fuels and lubricating oils on emissions, as well as topics for future research.

Evolution of the magnitude and spatial extent of the weekend ozone effect in California's South Coast Air Basin, 1981-2000.

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.

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.