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Species analyses have been performed on engine-out and tailpipe hydrocarbon mass emissions to help understand why fuels with higher T50 and/or T90 distillation temperatures produce higher engine-out and tailpipe hydrocarbon emissions and why fuels with higher T90 distillation temperatures produce higher engine-out and tailpipe specific reactivities. Species analyses were also performed to examine the effects of fuel sulfur level on engine-out and tailpipe species and specific reactivities. These analyses were performed on three different test-vehicle fleets representing varying levels of emissions control technology and the effect of emissions control technology was examined. Individual hydrocarbon species concentrations in both the engine-out and tailpipe were found to correlate linearly with the concentrations of the same species in the fuel, implying that a small fraction of the fuel escapes the combustion process and conversion over the catalyst.

Modal analyses have been performed on engine-out and tailpipe hydrocarbon mass emissions to help understand why fuels with higher T50 and/or T90 distillation temperatures produce somewhat higher engine-out hydrocarbon emissions and substantially higher tailpipe hydrocarbon emissions. Modal analyses were also performed to examine how increased fuel sulfur increases tailpipe hydrocarbon emissions and to identify which gasoline properties in this study are responsible for the lower tailpipe hydrocarbon emissions with reformulated gasolines. These analyses were performed on three different test vehicle fleets representing varying levels of emissions control technology. The modal analyses showed that the substantially higher tailpipe hydrocarbon emissions from fuels with high T50 and/or T90 distillation temperatures result primarily from these fuels producing substantially higher engine-out hydrocarbon emissions during the first cycle of the Federal Test Procedure (FTP).

Exhaust emissions were measured using a matrix of fuels designed to expand on prior AQIRP work by investigating potential interactive effects of fuel distillation parameters T50 and T90, and of T90 and fuel sulfur content. (T50 and T90 represent the temperature at which 50 or 90% of the fuel distills in a standard test.) This fuel matrix was used also to investigate whether fuel effects found in prior work with then-current vehicle technology can be expected to continue in future lower emission vehicles. An additional pair of fuels was included to extend the range of T50. The vehicles were half of the AQIRP Current fleet (ten vehicles) used in prior studies, and two new fleets of six vehicles each. One of the new fleets was designed to 1994 Federal Tier 1 standards, and the other was Advanced Technology prototypes targeted for lower emission levels of 1995 and later. A set of six fuels was tested in all three fleets.

The effect of gasoline olefin composition and content on urban ozone was estimated using the Urban Airshed Model (UAM), emission measurements for a base fuel, and projected emissions for two hypothetical fuels with reduced olefin content. The projected emissions for the hypothetical fuels were developed using regressions developed from Auto/Oil Air Quality Improvement Research Program (AQIRP) Phase I testing, a vapor headspace model and other information. Ozone modeling was conducted for Los Angeles in year 2010 and Dallas-Fort Worth and New York in year 2005. When all olefins were removed from the base fuel, the light-duty vehicle contribution to peak hourly ozone was reduced by 8 to 12%. This corresponds to a projected reduction of 0.6 to 0.8% in total peak ozone from all sources. Removing only light (C5) olefins provided 67 to 78% of the peak ozone benefit from removal of all olefins.

The analysis of data from the Auto/Oil Air Quality Improvement Research Program (AQIRP) study of the effect of aromatics, MTBE, olefins, and T90 on mass exhaust emissions from current (1989) vehicles was extended to include individual vehicles during individual operating modes. The results of the modal data analysis agree with and complement results which have been reported previously by AQIRP. Beyond this, attention is focused on three fuel compositional changes where the effect on emissions shows a reversal in sign depending on the vehicle operating mode chosen.

The chemistries controlling autoignition of primary reference fuels (n-heptane/isooctane binary mixtures) and binary olefin/paraffin mixtures have been inferred from experimental motored-engine measurements. For all n-heptane/isooctane and olefin/paraffin mixtures, each component of the mixture reacted via parallel intramolecular mechanisms with the only interactions being via small labile radicals. The octane qualities of the neat components appears to be dictated not by the initial reaction rate of the fuel, but by the reaction rate of the subsequent fuel-product reactions. In contrast, the blending octane quality of a component appears to be dictated more by the rate of the initial fuel reactions. The abnormally high blending octane qualities of olefins result from them having high rates of initial fuel reaction combined with slow rates of subsequent fuel-product reactions.

In this pilot study conducted by the Auto/Oil Air Quality Improvement Research Program, engine-out and tailpipe speciated hydrocarbon emissions were obtained for three vehicles operated over the Federal Test Procedure on two different fuels, both of which were speciated. The fates of the fuel species were traced across the engine and across the catalyst, and relationships were developed between engine-out and tailpipe hydrocarbon emissions and fuel composition. These relationships allowed separating the fuel's contribution to engine-out and tailpipe hydrocarbon emissions into two parts, unreacted fuel and partial oxidation products. Specific ozone reactivities and toxic air pollutants were analyzed for both engine-out and tailpipe emissions. Vehicle-to-vehicle, fuel-to-fuel, and bag-to-bag differences have been highlighted.

Autoignition chemistries of several paraffins, olefins, and aromatics were examined in a motored engine at different engine conditions. Paraffin chemistry was dominated by “negative-temperature coefficient” (NTC) behavior which became more pronounced at lower pressures, higher temperatures, and shorter reaction times. In contrast, olefin and aromatic chemistries did not exhibit NTC behavior. Measured pressures and calculated temperatures at fired octane rating conditions showed slightly lower pressures, higher temperatures, and lower reaction times at Motor octane rating conditions when compared to Research conditions. Therefore, paraffins would have a more pronounced NTC behavior under Motor rating conditions than under Research conditions.