Effects of reformulated gasoline and motor vehicle fleet turnover on emissions and ambient concentrations of benzene.

Gasoline-powered motor vehicles are a major source of toxic air contaminants such as benzene. Emissions from light-duty vehicles were measured in a San Francisco area highway tunnel during summers 1991, 1994-1997, 1999, 2001, and 2004. Benzene emission rates decreased over this time period, with a large (54 +/- 5%) decrease observed between 1995 and 1996 when California phase 2 reformulated gasoline (RFG) was introduced. We attribute this one-year change in benzene mainly to RFG effects: 36% from lower aromatics in gasoline that led to a lower benzene mass fraction in vehicle emissions, 14% due to RFG effects on total nonmethane organic compound mass emissions, and the remaining 4% due to fleet turnover. Fleet turnover effects accumulate over longer time periods: between 1995 and 2004, fleet turnover led to a 32% reduction in the benzene emission rate. A approximately 4 microg m(-3) decrease in benzene concentrations was observed at a network of ambient air sampling sites in the San Francisco Bay area between the late 1980s and 2004. The largest decrease in annual average ambient benzene concentrations (1.5 +/- 0.7 microg m(-3) or 42 +/- 19%) was observed between 1995 and 1996. The reduction in ambient benzene between spring/summer months of 1995 and 1996 due to phase 2 RFG was larger (60 +/- 20%). Effects of fuel changes on benzene during fall/winter months are difficult to quantify because some wintertime fuel changes had already occurred prior to 1995.

A Fuel-Based Approach to Estimating Motor Vehicle Cold-Start Emissions.

The temporary ineffectiveness of motor vehicle emission controls at startup causes emission rates to be much higher for a short period after starting than during fully warmed, or stabilized, vehicle operation. Official motor vehicle emission inventories estimate that excess emissions during cold-start operation contribute a significant fraction of all hydrocarbon, carbon monoxide (CO), and nitrogen oxide (NOx) emissions from California vehicles. In an effort to verify these estimates under real-world conditions, vehicle emissions were measured in an underground parking garage in Oakland, CA, during March 1997. Hot stabilized emissions were measured as vehicles arrived at the garage in the morning, and cold-start emissions were measured as vehicles exited in the afternoon; the incremental, or excess, emissions associated with vehicle starting were calculated by difference. Composite emissions from ~135 vehicles were sampled during each of six morning and six afternoon periods. Measured stabilized exhaust emissions were 19 ± 2 g nonmethane hydrocarbons (NMHC), 223 ± 17 g CO, and 8.6 ± 1.3 g NOx per gal of gasoline consumed. Cold-start emissions of 69 ± 2 g NMHC/gal, 660 ± 15 g CO/gal, and 27.8 ± 1.2 g NOx/gal were measured for vehicles spending an average of ~60 sec in the garage after starting in the afternoon. Using second-by-second emissions data from California's light-duty vehicle surveillance program, average fuel use during cold start was estimated to be ~0.07 gal, and the cold-start period was estimated to last for ~200 sec. When cold-start emission factors measured in the garage were scaled to represent the full 200-sec cold-start period, incremental start emission factors of 2.1 g NMHC, 16 g CO, and 2.1 g NOx per vehicle start were calculated. These emission factors are lower than those used by California's motor vehicle emission inventory model (MVEI 7G) by 45% for NMHC, 65% for CO, and 12% for NOx. This suggests that the importance of cold-start emissions may be overstated in current emission inventories. Overall, the composition of volatile organic compound (VOC) emissions measured during cold start was similar to that of hot stabilized VOC emissions. However, the weight fractions of unburned fuel and acetylene were higher during cold start than during hot stabilized driving.