A multipollutant evaluation of APEX using microenvironmental ozone, carbon monoxide, and particulate matter (PM2.5) concentrations measured in Los Angeles by the exposure classification project.

This paper describes an operational evaluation of the US Environmental Protection Agency's (EPA) Air Pollution Exposure Model (APEX). APEX simulations for a multipollutant ambient air mixture, i.e. ozone (O3), carbon monoxide (CO), and particulate matter 2.5 microns in diameter or less (PM2.5), were performed for two seasons in three study areas in central Los Angeles. APEX predicted microenvironmental concentrations were compared with concentrations of these three pollutants monitored in the Exposure Classification Project (ECP) study during the same periods. The ECP was designed expressly for evaluating exposure models and measured concentrations inside and outside 40 microenvironments. This evaluation study identifies important uncertainties in APEX inputs and model predictions useful for guiding further exposure model input data and algorithm development efforts. This paper also presents summaries of the concentrations in the different microenvironments.

High-end exposure relationships of volatile air toxics and carbon monoxide to community-scale air monitoring stations in Atlanta, Chicago, and Houston.

Evaporative and exhaust mobile source air toxic (MSAT) emissions of total volatile organic compounds, carbon monoxide, BTEX (benzene, toluene, ethylbenzene, and xylenes), formaldehyde, acetaldehyde, butadiene, methyl tertiary butyl ether, and ethanol were measured in vehicle-related high-end microenvironments (ME) under worst-case conditions plausibly simulating the >99th percentile of inhalation exposure concentrations in Atlanta (baseline gasoline), Chicago (ethanol-oxygenated gasoline), and Houston (methyl tertiary butyl either-oxygenated gasoline) during winter and summer seasons. High-end MSAT values as ratios of the corresponding measurements at nearby air monitoring stations exceeded the microenvironmental proximity factors used in regulatory exposure models, especially for refueling operations and MEs under reduced ventilation. MSAT concentrations were apportioned between exhaust and evaporative vehicle emissions in Houston where methyl tertiary butyl ether could be used as a vehicle emission tracer. With the exception of vehicle refueling operations, the results indicate that evaporative emissions are a minor component of high-end MSAT exposure concentrations.

Projected ozone trends and changes in the ozone-precursor relationship in the South Coast Air Basin in response to varying reductions of precursor emissions.

UNLABELLED: This study examined the effects of varying future reductions in emissions of oxides of nitrogen (NOx) and volatile organic compounds (VOC) on the location and magnitude of peak ozone levels within California's South Coast Air Basin (SoCAB or Basin). As ozone formation is currently VOC-limited in the Basin, model simulations with 2030 baseline emissions (-61% for NOx and -32% for VOC from 2008) predict 10-20% higher peak ozone levels (i.e., NOx disbenefit) in the western and central SoCAB compared with the 2008 base simulation. With additional NOx reductions of 50% beyond the 2030 baseline emissions (-81% from 2008), the predicted ozone levels are reduced by about 15% in the eastern SoCAB but remain comparable to 2008 levels in the western and central Basin. The Basin maximum ozone site shifts westward to more populated areas of the Basin and will result potentially in greater population-weighted exposure to ozone with even a relatively small shortfall in the required NOx reductions unless accompanied by additional VOC reductions beyond 2030 baseline levels. Once committed to a NOx-focused control strategy, NOx reductions exceeding 90% from 2008 levels will be necessary to attain the ozone National Ambient Air Quality Standards (NAAQS). The findings from this study and other recent work that the current VOC emission estimates are underestimated by about 50% suggest that greater future VOC reductions will be necessary to reach the projected 2030 baseline emissions. Increasing the base year VOC emissions by a factor of 1.5 result in higher 2008 baseline ozone predictions, lower relative response factors, and about 20% lower projected design values. If correct, these findings have important implications for the total and optimum mix of VOC and NOx emission reductions that will be required to attain the ozone NAAQS in the SoCAB. IMPLICATIONS: Results of this study indicate that ozone levels in the western and central SoCAB would remain the same or increase with even a relatively small shortfall in the projected NOx reductions under planned NOx-focused controls. This possibility, therefore, warrants a rigorous analysis of the costs and effects of varying reductions of VOC and NOx on the formation and combined health impacts of ozone and secondary particles. Given the nonlinearity of ozone formation, such analyses should include the implications of gradually increasing global background ozone concentrations and the Basin's topography and meteorology on the practical limits of alternative emission control strategies.

Concentrations of mobile source air pollutants in urban microenvironments.

Human exposures to criteria and hazardous air pollutants (HAPs) in urban areas vary greatly due to temporal-spatial variations in emissions, changing meteorology, varying proximity to sources, as well as due to building, vehicle, and other environmental characteristics that influence the amounts of ambient pollutants that penetrate or infiltrate into these microenvironments. Consequently, the exposure estimates derived from central-site ambient measurements are uncertain and tend to underestimate actual exposures. The Exposure Classification Project (ECP) was conducted to measure pollutant concentrations for common urban microenvironments (MEs) for use in evaluating the results of regulatory human exposure models. Nearly 500 sets of measurements were made in three Los Angeles County communities during fall 2008, winter 2009, and summer 2009. MEs included in-vehicle, near-road, outdoor and indoor locations accessible to the general public. Contemporaneous 1- to 15-min average personal breathing zone concentrations of carbon monoxide (CO), carbon dioxide (CO2), volatile organic compounds (VOCs), nitric oxide (NO), nitrogen oxides (NO(x)), particulate matter (< 2.5 microm diameter; PM2.5) mass, ultrafine particle (UFP; < 100 nm diameter) number black carbon (BC), speciated HAPs (e.g, benzene, toluene, ethylbenzene, xylenes [BTEX], 1,3-butadiene), and ozone (O3) were measured continuously. In-vehicle and inside/outside measurements were made in various passenger vehicle types and in public buildings to estimate penetration or infiltration factors. A large fraction of the observed pollutant concentrations for on-road MEs, especially near diesel trucks, was unrelated to ambient measurements at nearby monitors. Comparisons of ME concentrations estimated using the median ME/ambient ratio versus regression slopes and intercepts indicate that the regression approach may be more accurate for on-road MEs. Ranges in the ME/ambient ratios among ME categories were generally greater than differences among the three communities for the same ME category, suggesting that the ME proximity factors may be more broadly applicable to urban MEs. Implications: Estimates of population exposure to air pollutants extrapolated from ambient measurements at ambient fixed site monitors or exposure surrogates are prone to uncertainty. This study measured concentrations of mobile source air toxics (MSAT) and related criteria pollutants within in-vehicle, outdoor near-road, and indoor urban MEs to provide multipollutant ME measurements that can be used to calibrate regulatory exposure models.

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.

Spatial variations of particulate matter and air toxics in communities adjacent to the Port of Oakland.

The Bay Area Air Quality Management District (BAAQMD) sponsored the West Oakland Monitoring Study (WOMS) to provide supplemental air quality monitoring that will be used by the BAAQMD to evaluate local-scale dispersion modeling of diesel emissions and other toxic air contaminants for the area within and around the Port of Oakland. The WOMS was conducted during two seasonal periods of 4 weeks in summer 2009 and winter 2009/2010. Monitoring data showed spatial patterns of pollutant concentrations that were generally consistent with proximity to vehicle traffic. Concentrations of directly emitted pollutants were highest on heavily traveled roads with consistently lower concentrations away from the roadways. Pollutants that have higher emission rates from diesel trucks (nitric oxide, black carbon) tended to exhibit sharper gradients than pollutants that are largely associated with gasoline vehicles, such as carbon monoxide and volatile organic compounds, including benzene, toluene, ethylbenzene, and xylenes (BTEX). BTEX concentrations in West Oakland were similar to those measured at the three air toxics monitoring network sites in the Bay Area (San Francisco, Fremont, and San Jose). Aldehyde levels were higher in Fremont and San Jose than in West Oakland, reflecting greater contributions from photo-oxidation of hydrocarbons downwind of the Bay Area. A 2005 modeling-based health risk assessment of diesel particulate matter concentrations is consistent with aerosol carbon concentrations measured during the WOMS after adjusting for recent mitigation measures and improved estimates of heavy-duty truck traffic volumes.

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.

Concentrations of air toxics in motor vehicle-dominated environments.

We at the Desert Research Institute (DRI*) measured volatile organic compounds (VOCs), including several mobile-source air toxics (MSATs), particulate matter with a mass mean aerodynamic diameter < or = 2.5 pm (PM2.5), black carbon (BC), nitrogen oxides (NOx), particulate matter (PM), and carbon monoxide (CO) on highways in Los Angeles County during summer and fall 2004, to characterize the diurnal and seasonal variations in measured concentrations related to volume and mix of traffic. Concentrations of on-road pollutants were then compared to corresponding measurements at fixed monitoring sites. The on-road concentrations of CO and MSATs were higher in the morning under stable atmospheric conditions and during periods of higher traffic volumes. In contrast, BC concentrations, measured as particulate light absorption, were higher on truck routes during the midday sampling periods despite more unstable atmospheric conditions. Compared to the measurements at the three near-road sites, the 1-hour averages of on-road BC concentrations were as much as an order of magnitude higher. The peak 1-minute average concentrations were two orders of magnitude higher for BC and were between two and six times higher for PM2.5 mass. The on-road concentrations of benzene, toluene, ethylbenzene, and xylenes (BTEX) during the summer were 3.5 +/- 0.7 and 1.2 +/- 0.6 times higher during morning and afternoon commuting periods, respectively, compared to annual average 24-hour concentrations measured at air toxic monitoring network sites. These ratios were higher during the fall, with smaller diurnal differences (4.8 +/- 0.7 and 3.9 +/- 0.6 for morning and afternoon commuting periods, respectively). Ratios similar to those for BTEX were obtained for 1,3-butadiene (BD) and styrene. On-road concentrations of formaldehyde and acetaldehyde were up to two times higher than at air toxics monitoring sites, with fall ratios slightly higher than summer ratios. Chemical mass balance (CMB) receptor model calculations attributed the sum of BTEX almost exclusively to gasoline engine exhaust for on-road samples and all but 5% to 10% of the BTEX at the three near-road sites. CMB analysis attributed 46% to 52% (+/- 7) of the ambient total particulate carbon (TC) at the three near-road sites to diesel exhaust and 10% to 17% (+/- 7) to gasoline exhaust; it attributed about 90% of the ambient elemental carbon (EC) concentrations (measured as refractory carbon using the thermal evolution method) to diesel exhaust. Diesel particulate carbon (DPC) concentrations were estimated by multiplying the mean ratio of TC to EC from the source-dominated ambient samples collected on road on Terminal Island (1.30 +/- 0.28), which is located between the Long Beach and Los Angeles ports, with the measured ambient EC concentrations at the three near-road sites. DPC estimates from EC measurements correlate well with the diesel source contributions calculated with the CMB model. The indication from these apportionments that BC or EC is a good surrogate for diesel exhaust is further supported by the positive correlation of on-road BC concentrations with volumes of truck traffic. Traffic counts have been used in past health assessment studies as surrogates for estimating near-road exposure concentrations with appropriate weighting for proximity to the road. However, the results of this study show that it is necessary to account for the proportion of diesel trucks to total vehicular traffic because of the disproportionate contribution of diesel exhaust to BC and to directly emitted PM. Alternatively, easily measured pollutants such as CO and BC can serve as reasonable surrogates for MSATs (e.g., BTEX and BD) and DPC, respectively. Measuring CO and BC is a reasonably cost-effective approach to quantifying hot-spot exposure concentrations of MSATs that is perhaps more accurate than what is possible using only data from regional air quality monitoring stations or air quality modeling results.

Particulate emission factors for mobile fossil fuel and biomass combustion sources.

PM emission factors (EFs) for gasoline- and diesel-fueled vehicles and biomass combustion were measured in several recent studies. In the Gas/Diesel Split Study (GD-Split), PM(2.5) EFs for heavy-duty diesel vehicles (HDDV) ranged from 0.2 to ~2 g/mile and increased with vehicle age. EFs for HDDV estimated with the U.S. EPA MOBILE 6.2 and California Air Resources Board (ARB) EMFAC2007 models correlated well with measured values. PM(2.5) EFs measured for gasoline vehicles were ~two orders of magnitude lower than those for HDDV and did not correlate with model estimates. In the Kansas City Study, PM(2.5) EFs for gasoline-powered vehicles (e.g., passenger cars and light trucks) were generally <0.03 g/mile and were higher in winter than summer. EMFAC2007 reported higher PM(2.5) EFs than MOBILE 6.2 during winter, but not during summer, and neither model captured the variability of the measured EFs. Total PM EFs for heavy-duty diesel military vehicles ranged from 0.18±0.03 and 1.20±0.12 g/kg fuel, corresponding to 0.3 and 2 g/mile, respectively. These values are comparable to those of on-road HDDV. EFs for biomass burning measured during the Fire Laboratory at Missoula Experiment (FLAME) were compared with EFs from the ARB Emission Estimation System (EES) model. The highest PM(2.5) EFs (76.8±37.5 g/kg) were measured for wet (>50% moisture content) Ponderosa Pine needles. EFs were generally <20 g/kg when moisture content was <20%. The EES model agreed with measured EFs for fuels with low moisture content but underestimated measured EFs for fuel with moisture content >40%. Average EFs for dry chamise, rice straw, and dry grass were within a factor of three of values adopted by ARB in California's San Joaquin Valley (SJV). Discrepancies between measured and modeled emission factors suggest that there may be important uncertainties in current PM(2.5) emission inventories.

Evaluation of passive samplers for assessment of community exposure to toxic air contaminants and related pollutants.

The precision, accuracy, and sampling rates of Radiello and Ogawa passive samplers were evaluated in the laboratory using a flow-through chamber and under field conditions prior to their use in the 2007 Harbor Community Monitoring Study (HCMS), a saturation monitoring campaign in the communities adjacent to the Ports of Los Angeles and Long Beach. Passive methods included Radiello samplers for volatile organic compounds (benzene, toluene, ethylbenzene, xylenes, 1,3-butadiene), aldehydes (formaldehyde, acetaldehyde, acrolein) and hydrogen sulfide, and Ogawa samplers for nitrogen oxides and sulfur dioxide. Additional experiments were conducted to study the robustness of the passive sampling methods under variable ambient wind speed, sampling duration, and storage time before analysis. Our experimentally determined sampling rates were in agreement with the rates published by Radiello and Ogawa with the following exceptions: we observed a diffusion rate of 22.4 ± 0.1 mL/min for benzene and 37.4 ± 1.5 mL/min for ethylbenzene compared to the Radiello published values of 27.8 and 25.7 mL/min, respectively. With few exceptions, the passive monitoring methods measured one-week average ambient concentrations of selected pollutants with sensitivity and precision comparable to conventional monitoring methods averaged over the same period. Radiello Carbograph 4 VOC sampler is not suitable for the collection of 1,3-butadiene due to backdiffusion. Results for the Radiello aldehyde sampler were inconclusive due to lack of reliable reference methods for all carbonyl compounds of interest.

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.

Evaluations of the chemical mass balance method for determining contributions of gasoline and diesel exhaust to ambient carbonaceous aerosols.

The US. Department of Energy Gasoline/Diesel PM Split Study was conducted to assess the sources of uncertainties in using an organic compound-based chemical mass balance receptor model to quantify the relative contributions of emissions from gasoline (or spark ignition [SI]) and diesel (or compression ignition [CI]) engines to ambient concentrations of fine particulate matter (PM2.5) in California's South Coast Air Basin (SOCAB). In this study, several groups worked cooperatively on source and ambient sample collection and quality assurance aspects of the study but worked independently to perform chemical analysis and source apportionment. Ambient sampling included daily 24-hr PM2.5 samples at two air quality-monitoring stations, several regional urban locations, and along freeway routes and surface streets with varying proportions of automobile and truck traffic. Diesel exhaust was the dominant source of total carbon (TC) and elemental carbon (EC) at the Azusa and downtown Los Angeles, CA, monitoring sites, but samples from the central part of the air basin showed nearly equal apportionments of CI and SI. CI apportionments to TC were mainly dependent on EC, which was sensitive to the analytical method used. Weekday contributions of CI exhaust were higher for Interagency Monitoring of Protected Visual Environments (IMPROVE; 41+/-3.7%) than Speciation Trends Network (32+/-2.4%). EC had little effect on SI apportionment. SI apportionments were most sensitive to higher molecular weight polycyclic aromatic hydrocarbons (indeno[123-cd]pyrene, benzo(ghi)perylene, and coronene) and several steranes and hopanes, which were associated mainly with high emitters. Apportionments were also sensitive to choice of source profiles. CI contributions varied from 30% to 60% of TC when using individual source profiles rather than the composites used in the final apportionments. The apportionment of SI vehicles varied from 1% to 12% of TC depending on the specific profile that was used. Up to 70% of organic carbon (OC) in the ambient samples collected at the two fixed monitoring sites could not be apportioned to directly emitted PM emissions.

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.

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.

Emissions from charbroiling and grilling of chicken and beef.

Emission rates for fine particle (<2.5 microm) mass (PM2.5), carbon (organic/elemental), inorganic ions (SO4(2-), NO3-, NH4+), elements (primarily metals), and speciated organic compounds are reported for charbroiling hamburger, steak, and chicken. The PM2.5 rates for charbroiling meats ranged from 4.4 to 11.6 g/kg of uncooked meat in this study. No mass-emission rates are available from grilling, but the speciated organic data are available for these samples. Emission rates varied by type of appliance, meat, meat-fat content, and cooking conditions. High-fat hamburger cooked on an underfired charbroiler emitted the highest amount of PM2.5. The emissions were almost exclusively composed of organic carbon, with small amounts of elements and inorganic ions. Water-soluble K+ and Cl-, which are used as indicators of wood smoke in source apportionment studies, were also present in meat-cooking emissions. The speciated organic compounds that were measured include polycyclic aromatic hydrocarbons (PAHs), cholesterol, and the long-chain gamma-lactones. Charbroiling emissions yielded an average of approximately 3-5 times more PAHs, approximately 20 times more cholesterol, and approximately 10 times more lactones than grilling. These data were utilized in the ambient source apportionment analysis for the 1997 Northern Front Range Air Quality Study source apportionment.

Receptor modeling application framework for particle source apportionment.

Receptor models infer contributions from particulate matter (PM) source types using multivariate measurements of particle chemical and physical properties. Receptor models complement source models that estimate concentrations from emissions inventories and transport meteorology. Enrichment factor, chemical mass balance, multiple linear regression, eigenvector. edge detection, neural network, aerosol evolution, and aerosol equilibrium models have all been used to solve particulate air quality problems, and more than 500 citations of their theory and application document these uses. While elements, ions, and carbons were often used to apportion TSP, PM10, and PM2.5 among many source types, many of these components have been reduced in source emissions such that more complex measurements of carbon fractions, specific organic compounds, single particle characteristics, and isotopic abundances now need to be measured in source and receptor samples. Compliance monitoring networks are not usually designed to obtain data for the observables, locations, and time periods that allow receptor models to be applied. Measurements from existing networks can be used to form conceptual models that allow the needed monitoring network to be optimized. The framework for using receptor models to solve air quality problems consists of: (1) formulating a conceptual model; (2) identifying potential sources; (3) characterizing source emissions; (4) obtaining and analyzing ambient PM samples for major components and source markers; (5) confirming source types with multivariate receptor models; (6) quantifying source contributions with the chemical mass balance; (7) estimating profile changes and the limiting precursor gases for secondary aerosols; and (8) reconciling receptor modeling results with source models, emissions inventories, and receptor data analyses.

Assessment of Nontailpipe Hydrocarbon Emissions from Motor Vehicles.

This report evaluates tailpipe and nontailpipe hydrocarbon (HC) emissions from light-duty spark-ignition (SI) vehicles. The sources of information were unpublished data sets, generated mainly from 1990 through 1994, on emissions from volunteer fleets of in-use vehicles in chassis dynamometer and sealed housing for evaporative determination tests, and published chemical mass balance (CMB) source apportionments of HC in roadway tunnels and in urban air. The nontailpipe emissions evaluated comprise running-loss, hot soak, diurnal emissions, and resting-loss emissions. Relations between pressure and purge test failures and actual nontailpipe emissions were also examined.