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Copolymer materials have been used for the collection of vehicle exhaust gas samples since the inception of regulatory standards. Some of these copolymers contain N,N-dimethylacetamide (DMA), which is added to improve the physical properties of the copolymer and eliminate manufacturing problems. DMA is highly soluble in water, and in effect is rinsed from the emission bag surface by humid exhaust gas samples. This study shows that DMA can thus incorrectly add to test vehicle overall hydrocarbon emissions. The DMA contribution can be significant for lower level emission vehicles. This study introduces a new bag material, KYNAR®, which significantly reduces this interference.

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.

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.

Near-infrared spectroscopy and chemometric data analysis techniques have been used to predict the chemical and physical properties of gasolines using a set of 359 commercial gasolines from 23 U.S. cities. These methods can estimate ten or more important fuel properties in a few minutes with reproducibilities equivalent to the lengthy ASTM standard procedures. Potential applications include field monitoring of gasolines and on-board sensors of fuel parameters.

Because of the increasing use of rubber formulations and plastics by the automotive industry, analytical methods are continually being sought for quality control and receiving inspection. The application of the thermal analysis technique, known as thermogravimetry, to the problems of fast quality control analysis is discussed. Specific examples in the areas of relative thermal stability, analysis of additives, and compositional analysis of formulations are presented.