Detailed Speciation of Intermediate Volatility and Semivolatile Organic Compound Emissions from Gasoline Vehicles: Effects of Cold-Starts and Implications for Secondary Organic Aerosol Formation.

Over the past two decades vehicle emission standards in the United States have been dramatically tightened with the goal of reducing urban air pollution. Secondary organic aerosol (SOA) is the dominant contributor to urban organic aerosol. Experiments were conducted at the California Air Resources Board Haagen-Smit Laboratory to characterize exhaust organics from 20 gasoline vehicles recruited from the California in-use fleet. The vehicles spanned a wide range of emission certification standards. We comprehensively characterized intermediate volatility and semivolatile organic compound emissions using thermal desorption two-dimensional gas-chromatography-mass-spectrometry with electron impact (GC × GC-EI-MS) and vacuum-ultraviolet (GC × GC-VUV-MS) ionization. Single-ring aromatic compounds with unsaturated C4 and C5 substituents contribute a large fraction of the intermediate volatility organic compound (IVOC) emissions in gasoline vehicle exhaust. The analyses of quartz filters used in GC × GC-VUV-MS show that primary organic aerosol emissions were dominated by motor oil. We combined our new emissions data with published SOA yield parametrizations to estimate SOA formation potential. After 24 h of oxidation, IVOC emissions contributed 45% of  SOA formation;  BTEX compounds (benzene, toluene, xylenes, and ethylbenzene), 40%;  other VOC aromatics, 15%. The composition of IVOC emissions was consistent across the test fleet, suggesting that future reductions in vehicular emissions will continue to reduce SOA formation and ambient particulate mass levels.

A case study of real-world tailpipe emissions for school buses using a 20% biodiesel blend.

Numerous laboratory studies report carbon monoxide, hydrocarbon, and particulate matter emission reductions with a slight nitrogen oxides emission increase from engines operating with biodiesel and biodiesel blends as compared to using petroleum diesel. We conducted a field study on a fleet of school buses to evaluate the effects of biodiesel use on gaseous and particulate matter fuel-based emission factors under real-world conditions. The field experiment was carried out in two phases during winter 2004. In January (phase I), emissions from approximately 200 school buses operating on petroleum diesel were measured. Immediately after the end of the first phase measurement period, the buses were switched to a 20% biodiesel blend. Emission factors were measured again in March 2004 (phase II) and compared with the January emission factors. To measure gaseous emission factors we used a commercial gaseous remote sensor. Particulate matter emission factors were determined with a combination of the gaseous remote sensor, a Lidar (light detection and ranging), and transmissometer system developed at the Desert Research Institute of Reno, NV, U.S.A. Particulate matter emissions from school buses significantly increased (up to a factor of 1.8) after the switch from petroleum diesel to a 20% biodiesel blend. The fuel used during this campaign was provided by a local distributor and was independently analyzed at the end of the on-road experiment. The analysis found high concentrations of free glycerin and reduced flash points in the B 100 parent fuel. Both measures indicate improper separation and processing of the biodiesel product during production. The biodiesel fuels used in the school buses were not in compliance with the U.S.A. ASTM D6751 biodiesel standard that was finalized in December of 2001. The U.S.A. National Biodiesel Board has formed a voluntary National Biodiesel Accreditation Program for producers and marketers of biodiesel to ensure product quality and compliance with the ASTM standard. The results of our study underline the importance of the program since potential emission benefits from biodiesel may be reduced or even reversed without appropriate fuel quality control on real-world fuels.