Search Results

As automotive exhaust emission levels reduce, there is a need for increased sensitivity of the NOx measurement. This paper documents work performed to increase the sensitivity of the existing Rosemount NGA 2000 CLD Analyzer. The effects of sample flow rate, ozone flow rate and ozone supply gas were explored. Limit of Detection (LOD) and Converter Efficiency were evaluated. The goal of this optimization has been to provide a cost effective and expeditious method to improve the low level NOx measurement. Changing the ozone generator supply gas from air to oxygen and increasing the sample and ozone flow rates resulted in a LOD improvement from 17 ppb to 8 ppb.

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).

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.

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

Certification of flex-fueled vehicles to US Environmental Protection Agency (EPA) and California Air Resources Board (CARB) emission standards requires a flame ionization detector (FID) analysis for hydrocarbons, plus a separate analysis for alcohols. Alcohol analysis methods, such as those found in the California Non-Methane Organic Gas (NMOG) Test Procedures and in the Code of Federal Regulations (40 Part 86), involve the bubbling of vehicle sample gas (exhaust or evaporative) through sample impingers filled with water. The water is then analyzed by gas chromatography (GC) equipped with a FID. This method requires significant manual sample handling and transport, and may take many hours for analysis to be complete. After analysis is completed, the vehicle test results are post-processed, sometimes manually, to generate the final sample results. This report describes the direct bag analysis of ethanol with a photoacoustic gas analyzer.

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.

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.