Weekday/weekend differences in OH reactivity with VOCs and CO in Baltimore, Maryland

This study compared the first-order frequencies for OH associated with volatile organic compounds (VOCs) and CO (hereafter called OH reactivity with VOCs or CO), the product of the VOC or CO concentration, and their respective kOH value, on an average weekday with that on an average weekend day at a core urban site in Baltimore, MD. The average daytime concentrations were calculated for each of the 55 available Photochemical Assessment Monitoring Station (PAMS) VOCs using data from the Baltimore site. The data were sorted in descending order to highlight the important species based on concentration. The OH reactivity with VOCs was sorted in descending order to identify the important species based on the magnitude of the OH reactivity. A similar process was followed for the OH reactivity with CO. The contribution of the significant species to the weekday/weekend difference in OH reactivity was examined. The OH reactivity with C5H8 was the largest among the OH reactivity with the PAMS' VOCs and was the same on the weekday and weekend. The weekday/weekend difference in OH reactivity with VOCs was entirely due to differences in concentrations of the anthropogenic VOCs. The OH reactivity with VOCs was 11% larger on the weekday. When OH reactivity with CO was included, the OH reactivity was 13% larger on the weekday.     

The Spatial Variation of the Weekday/Weekend Differences in the Baltimore Area

ABSTRACT

This study examined the spatial distribution of the weekday/weekend difference in Baltimore, MD, and vicinity. The difference in Baltimore was characterized by having ~39% more NO_x , ~59% more CO, and ~27% more volatile organic compounds (VOCs) on the average weekday, but there was ~13% more O₃ on the weekend day. Spatially, the difference was elongated in the northeast-southwest direction. It decreased from 13% more O₃ in Baltimore to 6% at ~20 km west of Baltimore and to 4% at ~40 km south of Baltimore. It also appeared to decrease to the east, but the magnitude of the decrease could not be determined because of the lack of data east of the Chesapeake Bay. However, the difference increased to the north, reaching a value of almost 18% at a northern Delaware site.     

The spatial variation of the weekday/weekend differences in the Baltimore area

This study examined the spatial distribution of the weekday/weekend difference in Baltimore, MD, and vicinity. The difference in Baltimore was characterized by having approximately 39% more NOx, approximately 59% more CO, and approximately 27% more volatile organic compounds (VOCs) on the average weekday, but there was approximately 13% more O3 on the weekend day. Spatially, the difference was elongated in the northeast-southwest direction. It decreased from 13% more O3 in Baltimore to 6% at approximately 20 km west of Baltimore and to 4% at approximately 40 km south of Baltimore. It also appeared to decrease to the east, but the magnitude of the decrease could not be determined because of the lack of data east of the Chesapeake Bay. However, the difference increased to the north, reaching a value of almost 18% at a northern Delaware site.     

Day-of-Week Patterns of Particulate Matter and Its Chemical Components at Selected Sites in California

Abstract

This paper analyzes day-of-week variations in concentrations of particulate matter (PM) in California. Because volatile organic compounds (VOCs) and oxides of nitrogen (NO_x) are not only precursors of ozone (O₃) but also of secondary PM, it is useful to know whether the variations by day of week in these precursors are also evident in PM data. Concentrations of PM ≤10 μm (PM₁₀) and ≤2.5[H9262]m in aerodynamic diameter (PM_2.5) were analyzed. PM concentrations exhibit a general weekly pattern, with the maximum occurring late in the workweek and the minimum occurring on weekends (especially Sunday); however, this pattern does not prevail at all sites and areas. PM nitrate (NO₃ ^-) data from Size Selective Inlet (SSI) samplers in the South Coast Air Basin (SoCAB) tend to be somewhat lower on weekends compared with weekdays. During 1988–1991, the weekend average was lower than the weekday average at 8 of 13 locations, with an average decrease of 1%. During 1997–2000, the weekend average was lower than the weekday average at 10 of 13 locations, with an average decrease of 6%. The weekend averages are generally lower than weekday averages for sulfates, organic carbon, and elemental carbon. Because heavy-duty trucks typically represent a major source of elemental carbon, the weekend decrease in heavy-duty truck traffic may also result in a decrease in ambient elemental carbon concentrations.     

Spatial mapping of VOC and NOx-limitation of ozone formation in central California

Ambient aerometric data were used to predict whether ozone formation at specific times and locations in central California was limited by the availability of volatile organic compounds (VOC) or oxides of nitrogen (NO_x). The predictions were compared with differences between mean weekday and weekend peak ozone values. The comparison with weekend and weekday ozone levels provided a means for empirically investigating the effects of VOC and NO_x reductions on ozone formation, because the relative proportions and levels of ozone precursor species were significantly different on weekends than on weekdays. Weekend NO_x levels averaged 27 percent lower than weekday levels at the time of the peak ozone hour. Daytime weekend levels of VOC species were also consistently lower than weekday values throughout the region, though the differences between weekends and weekdays were not always statistically significant (p<0.05). Site-to-site differences between weekend and weekday mean peak hourly ozone were related to whether ozone formation was VOC- or NO_x-limited.     

Total OH reactivity and VOC analyses for gasoline vehicular exhaust with a chassis dynamometer

Total OH reactivity for the exhaust gas of gasoline vehicles was measured for the first time under nine different driving conditions with a chassis dynamometer at the National Institute for Environmental Studies (NIES). Along with the total OH reactivity measurements, analysis of trace species such as CH₄, CO, NO, NO₂, and 56 kinds of volatile organic compounds (VOCs), including two aldehydes, was carried out. The ratio of alkanes to alkenes in the exhaust gas turned out to depend on the condition of the driving cycles. There were a considerable number of unidentified peaks obtained during GC analysis. About 15–30% of the total carbon was unidentified species. The chemical compositions of vehicular exhaust were found to depend on the temperature of the engine or catalysts. The contribution of OH reactivity to the species obtained depended on the temperature condition for the engine. The calculated total OH reactivity for VOCs was compared with ozone formation potential (OFP) and it turned out that there are in good correlation, while the correlation for “Cold” start deviates from that for “Hot” start. The measured and calculated OH reactivities were compared with each other. For all driving cycles, the calculated OH reactivity was confirmed to be an underestimation, implying the existence of unknown species in the exhaust gas. The percentage contribution of OH reactivity to the unknown species during “Cold” start was about 17.5%, which was almost the same as that for “Hot” start at 17.0%. However, the absolute value of OH reactivity for “Cold” start was about ten times higher than that for “Hot” start.     

Differences between Weekday and Weekend Air Pollutant Levels in Southern California

Abstract

Ambient air quality data were analyzed to empirically evaluate the effects of reductions of volatile organic compounds (VOCs) and oxides of nitrogen (NO_x) emissions on weekday and weekend levels of ozone (O₃; 1991–1998) and particulate NO₃ ^- (1980–1999) in southern California. Despite significantly lower O₃ precursor levels on weekends, 20 of 28 South Coast Air Basin (SoCAB) sites (28 of all 78 southern California sites) showed statistically significant higher mean O₃ levels on Sundays than on weekdays (p < 0.01); 49 of the remaining 50 sites showed no significant differences between mean weekday and Sunday peak O₃ levels. We also observed no statistically significant differences between mean weekday and weekend concentrations of particulate NO₃ ^- or nitric acid (HNO₃, the precursor of particulate NO₃ ^-). Averaged over sites, the mean Sunday NO_x and nonmethane hydrocarbon concentrations were 25–41% and 16–30% lower, respectively, than on weekdays. Site-to-site differences between weekend and weekday mean peak hourly O₃ levels were related to whether O₃ formation was limited by the availability of NO_x. A thermodynamic equilibrium model predicts that particulate NO₃ ^- levels would decrease in response to a reduction of HNO₃, and that particulate ammonium NO₃ ^- formation was not limited by the availability of ammonia. The similarity of mean weekday and weekend levels of NO₃ ^- therefore did not result from limitations on the formation of particulate NO₃ ^- from its precursor, HNO₃.     

Weekday vs. Weekend Ambient Ozone Concentrations: Discussion and Hypotheses with Focus on Northern California

Abstract

Since the early 1970s, researchers and data analysts have reported differences between weekday and weekend ozone concentrations, with higher ozone concentrations occurring on Sundays in some locations. At that time, the phenomenon was referred to as the “Sunday effect.” In the late 1980s, additional papers focused on weekday/weekend differences in air quality in the South Coast (Los Angeles) Air Basin.

Analyses of ozone concentrations measured at a number of locations in northern California reveal that average ozone concentrations are frequently higher on weekends than on weekdays. Violations of the California 0.09 ppm 1-hour air quality standard for ozone also occur in disproportionately greater frequency on weekends. We hypothesize that this phenomenon is based largely on the differences between weekday and weekend emission patterns. We believe that the observed differences may provide information regarding which pollutant reduction strategy, NO_x or ROG control, may be more effective in reducing ambient ozone concentrations. For the northern California region, the presence of higher weekend ozone concentrations suggests the need for ROG control is greater than for NO_x control. If both NO_x and ROG are to be controlled, it is important to understand the interdependence of the two pollutants in forming ozone. With the current uncertainty and debate regarding official vehicular emission inventories, this phenomenon emphasizes the importance of using observation-based data to examine ambient pollution and emission relationships. This natural experiment of varying emissions provides an interesting test case for sophisticated air pollution model performance and evaluation.

Using a Bay Area emission inventory and an estimate of its change from weekday to weekend, combined with a generic Empirical Kinetic Modeling Approach (EKMA) diagram, we demonstrate the weekend effect. In addition, changes in the Bay Area emission inventory from 1980 to 1990, when combined with the EKMA diagram, also show why the weekend effect is more evident in the 1990s.

It is our hypothesis that the presence of the weekend effect, positive or negative, combined with changes in emission changes, provides a simple clue to whether an area is NO_xor ROG limited with respect to ozone formation.     

Field Method Comparison between Passive Air Samplers and Continuous Monitors for VOCs and NO2 in El Paso,Texas

Abstract

This study evaluates the performance of Model 3300 Ogawa Passive Nitrogen Dioxide (NO₂) Samplers and 3M 3520 Organic Vapor Monitors (OVMs) by comparing integrated passive sampling concentrations to averaged hourly NO₂ and volatile organic compound (VOC) measurements at two sites in El Paso, TX. Sampling periods were three time intervals (3-day weekend, 4-day weekday, and 7-day weekly) for three consecutive weeks. OVM concentrations were corrected for ambient pressure to account for higher elevation. Precise results (<5% relative standard deviation, RSD) were found for NO₂ measurements from collocated Ogawa samplers. Reproducibility was lower from duplicate OVMs for BTEX (benzene, toluene, ethylbenzene, and xylene isomers) VOCs (≥7% RSD for 2-day samples) with better precision for longer sampling periods. Comparison of Ogawa NO₂ samplers with chemiluminescence measurements averaged over the same time period suggested potential calibration problems with the chemiluminescence analyzer. For BTEX species, generally good agreement was obtained between OVMs and automated-gas chromatograph (auto-GC) measurements. The OVMs successfully tracked increasing levels of VOCs recorded by the auto-GCs.     

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

Abstract

We evaluated day-of-week differences in mean concentrations of ozone (O₃) precursors (nitric oxide [NO], nitrogen oxides [NO_x], carbon moNO_xide [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, NO_x, 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 NO_x 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, NO_x, CO, and VOCs declined by 65, 49, 28, and 19%, respectively, from Wednesdays to Sundays (median site responses). Despite the large reductions in ambient NO_x and moderate reductions in ambient CO and VOC concentrations on weekends, ozone and particulate matter (PM) nitrate did not exhibit large changes from week-days 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.     

NMOC,ozone, and organic aerosol in the southeastern United States, 1999–2007: 1. Spatial and temporal variations of NMOC concentrations and composition in Atlanta,Georgia

Volatile organic compounds (VOCs) are emitted from anthropogenic and natural (biogenic) sources into the atmosphere. Characterizing their ambient mixing ratios or concentrations is a challenge because VOCs comprise hundreds of species, and accurate measurements are difficult. Long-term hourly and daily-resolution data have been collected in the metropolitan area of Atlanta, Georgia, a major city dominated by motor vehicle emissions. A series of observations of daily, speciated C₂–C₁₀ non-methane organic compounds (NMOC) and oxygenated hydrocarbons (OVOC) in mid-town Atlanta (Jefferson Street, JST) are compared with data from three urban-suburban sites and a nearby non-urban site. Annual-average mixing ratios of NMOC and OVOC at JST declined from 1999 through 2007. Downward trends in NMOC, CO, and NO_y corroborate expected emission changes as reflected in emission inventories for Atlanta’s Fulton County. Comparison of the JST NMOC composition with data from roadside and tunnel sampling reveals similarities to motor vehicle dominated samples. The JST annual average VOC-OH reactivities from 1999 to 2007 were relatively constant compared with the decline in annual-average NMOC mixing ratios. Mean reactivity at JST, in terms of concentration*k_OH, was approximately 40% alkenes, 22% aromatics, 16% isoprene and 6% other biogenics, 13% C₇–C₁₀ alkanes and 3% C₂-C₆ alkanes, indicating that biogenic NMOCs are important but not dominant contributors to the urban reactive NMOC mix. In contrast, isoprene constituted ～50% of the VOC-OH reactivities at two non-urban sites. Ratios of 24-hour average CO/benzene, CO/isopentane, and CO/acetylene concentrations indicate that such species are relatively conserved, consistent with their low reactivity. Ratios of more-reactive to less-reactive species show diurnal variability largely consistent with expected emission patterns, transport and mixing of air, and chemical processing.     

Day-of-week patterns of particulate matter and its chemical components at selected sites in California

This paper analyzes day-of-week variations in concentrations of particulate matter (PM) in California. Because volatile organic compounds (VOCs) and oxides of nitrogen (NOx) are not only precursors of ozone (O3) but also of secondary PM, it is useful to know whether the variations by day of week in these precursors are also evident in PM data. Concentrations of PM < or = 10 microm (PM10) and < or = 2.5 microm in aerodynamic diameter (PM2.5) were analyzed. PM concentrations exhibit a general weekly pattern, with the maximum occurring late in the workweek and the minimum occurring on weekends (especially Sunday); however, this pattern does not prevail at all sites and areas. PM nitrate (NO3-) data from Size Selective Inlet (SSI) samplers in the South Coast Air Basin (SoCAB) tend to be somewhat lower on weekends compared with weekdays. During 1988-1991, the weekend average was lower than the weekday average at 8 of 13 locations, with an average decrease of 1%. During 1997-2000, the weekend average was lower than the weekday average at 10 of 13 locations, with an average decrease of 6%. The weekend averages are generally lower than weekday averages for sulfates, organic carbon, and elemental carbon. Because heavy-duty trucks typically represent a major source of elemental carbon, the weekend decrease in heavy-duty truck traffic may also result in a decrease in ambient elemental carbon concentrations.     

Weekday/Weekend Ozone Differences: What Can We Learn from Them?

Abstract

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

Vehicle emissions of radical precursors and related species observed in the 2009 SHARP campaign

The 2009 Study of Houston Atmospheric Radical Precursors (SHARP) field campaign had several components that yielded information on the primary vehicular emissions of formaldehyde (HCHO) and nitrous acid (HONO), in addition to many other species. Analysis of HONO measurements at the Moody Tower site in Houston, TX, yielded emission ratios of HONO to the vehicle exhaust tracer species NO_x and CO of 14 pptv/ppbv and 2.3 pptv/ppbv, somewhat smaller than recently published results from the Galleria site, although evidence is presented that the Moody Tower values should be upper limits to the true ratios of directly emitted HONO, and are consistent with ratios used in current standard emissions models. Several other Moody Tower emission ratios are presented, in particular a value for HCHO/CO of 2.4 pptv/ppbv. Considering only estimates of random errors, this would be significantly lower than a previous value, though the small sample size and possible systematic differences should be taken into account. Emission factors for CO, NO_x, and HCHO, as well as various volatile organic compounds (VOCs), were derived from mobile laboratory measurements both in the Washburn Tunnel and in on-road exhaust plume observations. These two sets of results and others reported in the literature all agree well, and are substantially larger than the CO, NO_x, and HCHO emission factors derived from the emission ratios reported from the Galleria site.

Implications: Emission factors for the species measured in the various components of the 2009 SHARP campaign in Houston, TX, including HCHO, HONO, CO, CO₂, nitrogen oxides, and VOCs, are needed to support regional air quality monitoring. Components of the SHARP campaign measured these species in several different ways, each with their own potential for systematic errors and differences in vehicle fleets sampled. Comparisons between data sets suggest that differences in sampling place and time may result in quite different emission factors, while also showing that different vehicle mixes can yield surprisingly similar emission factors.     

The Effect of Reformulated Gasoline on Ambient Carbon Monoxide Concentrations in Southeastern Wisconsin

Abstract

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 ～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.     

Real-world vehicle emissions and VOCs profile in the Taipei tunnel located at Taiwan Taipei area

An in situ field experiment was conducted in a highway road tunnel in the Taipei City to determine the motor vehicle emission factors (EF) of different kinds of air pollution species. These are carbon monoxide (CO), oxides of nitrogen (NO_x), non-methane hydrocarbons (NMHC) and VOCs species. About 56 species of VOCs were sampled by canister sampler and followed by the GC-MS analyzing. Furthermore, the tunnel-drafting rate was determined by SF₆ tracer method.The EF for the highway vehicles determined from this experiment are 3.64, 0.90, 0.44 and 0.24 gm km⁻¹ veh⁻¹ for CO, NO_x, NMHC and the totally measured VOCs, respectively. A comparison of the EFs from the road tunnel experiment to the estimates by the USEPA MOBILE5b (M5b) and the modified Taiwan EPA MOBILE-TAIWAN2.0 (MT2.0) provides a first-hand evaluation of the model characteristics. M5b and MT2.0 both tend to underpredict CO by 10% and 20%, respectively. While M5b overpredicts NO_x and NMHC by 40% and 20%, respectively; MT2.0 has fairly good predictions for these two species. From the GC-MS analysis of the canister samples, it was found that the most abundant species from the traffic-emitted VOCs in Taipei road tunnel are toluene, ethene and 1,2,4-trimethyl-benzene (1,2,4-TMB) by the weight basis. However, ethene, acetylene and toluene are the most abundant in VOCs based on volume. The VOCs’ weight composition in terms of the carbon bond classification is 28% by the paraffins, 33% by the olefins and 39% by the aromatics, respectively. In order to evaluate the ozone formation potential from the typical road emission in Taipei area, the maximum increment reactivity is calculated. It was found that about 1015 mg of O₃ is induced by per vehicle per kilometer traveled emission. Among them, ethene, 1,2,4-TMB and propene from the road vehicle's emission contribute most to the ozone-formation reactivity.     

Differences in airborne particle and gaseous concentrations in urban air between weekdays and weekends

Airborne particle number concentrations and size distributions as well as CO and NO_x concentrations monitored at a site within the central business district of Brisbane, Australia were correlated with the traffic flow rate on a nearby freeway with the aim of investigating differences between weekday and weekend pollutant characteristics. Observations over a 5-year monitoring period showed that the mean number particle concentration on weekdays was (8.8±0.1)×10³ cm⁻³ and on weekends (5.9±0.2)×10³ cm⁻³—a difference of 47%. The corresponding mean particle number median diameters during weekdays and weekends were 44.2±0.3 and 50.2±0.2 nm, respectively. The differences in mean particle number concentration and size between weekdays and weekends were found to be statistically significant at confidence levels of over 99%. During a 1-year period of observation, the mean traffic flow rate on the freeway was 14.2×10⁴ and 9.6×10⁴ vehicles per weekday and weekend day, respectively—a difference of 48%. The mean diurnal variations of the particle number and the gaseous concentrations closely followed the traffic flow rate on both weekdays and weekends (correlation coefficient of 0.86 for particles). The overall conclusion, as to the effect of traffic on concentration levels of pollutant concentration in the vicinity of a major road (about 100 m) carrying traffic of the order of 10⁵ vehicles per day, is that about a 50% increase in traffic flow rate results in similar increases of CO and NO_x concentrations and a higher increase of about 70% in particle number concentration.     

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

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 CO/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.     

An Alternative Approach to Photochemical Ozone Creation Potentials Applied under European Conditions

ABSTRACT

Photochemical ozone creation potential (POCP) values for 83 different volatile organic compounds (VOCs), including CO and CH₄, were calculated under different environmental conditions representative for Europe. These calculations show that variations in POCP values are large between different types of chemical environments and that POCP values for VOCs should be presented as ranges instead of single values. POCP ranges are based on the extremes of the POCP values and are defined with the intention to include all POCP values an individual VOC will obtain in any European environment where O₃ formation is of environmental concern. The POCP ranges indicate large differences in O₃ production between individual VOCs, which justifies the use of this ranking scale instead of treating all VOCs as a homogeneous group of species in abatement strategies.

Both the average O₃ production over 96 hr and the maximum contribution to the O₃ concentration were studied. The most efficient O₃ producers were found to be iso-prene, 2-methyl-2-butene, and acrolein. As a group, the alkenes are the most potent O₃ producers, followed by higher alkanes and then the aromatics. The calculated values show a good agreement with previously calculated POCP values under northern European conditions.     

Weekday-Weekend Pollutant Studies of the Los Angeles Basin

Pollutant data from the Los Angeles Basin were analyzed for weekday-weekend differences for the smog months of June through September 1972 and 1973. The pollutants investigated were oxidant, NO, NO₂, total hydrocarbons (HC), CO, and particulates. In order to maintain the diurnal variation, the concentration percentiles were calculated for each weekday and weekend hour.