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The Automotive Industry/Government Emissions Research CRADA (AIGER) has been working to develop a new methodology for the direct determination of nonmethane hydrocarbons (DNMHC) in vehicle testing. This new measurement technique avoids the need for subtraction of a separately determined methane value from the total hydrocarbon measurement as is presently required by the Code of Federal Regulations. This paper will cover the historical aspects of the development program, which was initiated in 1993 and concluded in 2002. A fast, gas chromatographic (GC) column technology was selected and developed for the measurement of the nonmethane hydrocarbons directly, without any interference or correction being caused by the co-presence of sample methane. This new methodology chromatographically separates the methane from the nonmethane hydrocarbons, and then measures both the methane and the backflushed, total nonmethane hydrocarbons using standard flame ionization detection (FID).

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.

The ozone forming potential (OFP) and specific reactivity (SR) of tailpipe exhaust are among the regulated factors that determine the environmental impact of a motor vehicle. OFP and SR measurements require a lengthy determination of about 160 non-methane hydrocarbon species. A rapid gas chromatography (GC) instrument has been constructed to separate both the light (C2 - C4) and the midrange (C5 - C12) hydrocarbons in less than 10 minutes. The limit of detection was about 0.002 parts per million carbon (ppmC). Twelve exhaust samples from two vehicles were analyzed to compare the rapid GC method with the standard GC method, which required 40-minute analyses on two different instruments. Speciation and reactivity data from the two methods were comparable. The increased sample throughput of rapid GC promises to improve OFP and SR measurements, particularly when good statistical data are necessary to insure accurate, precise results for low emission vehicles