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Analytical methods for determining individual aldehyde, ketone, and alcohol emissions from gasoline-, methanol-, and variable-fueled vehicles are described. These methods were used in the Auto/Oil Air Quality Improvement Research Program to provide emission data for comparison of individual reformulated fuels, individual vehicles, and for air modeling studies. The emission samples are collected in impingers which contain either 2,4-dinitrophenylhydrazine solution for the aldehydes and ketones or deionized water for the alcohols. Subsequent analyses by liquid chromatography for the aldehydes and ketones and gas chromatography for the alcohols utilize autoinjectors and computerized data systems which permit high sample throughput with minimal operator intervention. The quality control procedures developed and interlaboratory comparisons conducted as part of this program are also described.

Analytical procedures for the speciation of hydrocarbons and oxygenates (ethers, aldehydes, ketones and alcohols) in vehicle evaporative and tailpipe exhaust emissions have been improved for Phase II studies of the Auto/Oil Air Quality Improvement Research Program (AQIRP). One gas chromatograph (GC) was used for measurement of C1-C4 species and a second GC for C4-C12 species. Detection limits for this technique are 0.005 ppm C or 0.1 mg/mile exhaust emission level at a chromatographic signal-to-noise ratio of 3/1, a ten-fold improvement over the Phase I technique. The Phase I library was modified to include additional species for a total of 154 species. A 23-component gas standard was used to establish a calibration scale for automated computer identification of species. This method identifies 95±3% of the total hydrocarbon mass measured by GC for a typical exhaust sample. Solid adsorbent cartridges or impingers were used to collect aldehydes and ketones.

An analytical method for the determination of hydrocarbon and ether emissions from gasoline-, methanol-, and flexible-fueled vehicles is described. This method was used in Phase I of the Auto/Oil Air Quality Improvement Research Program to provide emissions data for various vehicles using individual reformulated gasolines and alternate fuels. These data would then be used for air modeling studies. Emission samples for tailpipe, evaporative, and running loss were collected in Tedlar bags. Gas chromatographic analysis of the emissions samples included 140 components (hydrocarbons, ethers, alcohols and aldehydes) between C1 and C12 in a single analysis of 54-minutes duration. Standardization, quality control procedures, and inter-laboratory comparisons developed and completed as part of this program are also described.