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Although the intent of the SHED test (Sealed Housing for Evaporative Determination) is to measure evaporative fuel losses, the SHED sampling methodology in fact measures hydrocarbons from all vehicle and test equipment sources. Leakage of air conditioning (AC) refrigerant is one possible non-fuel source contributing to the SHED hydrocarbon measurement. This report describes a quick and relatively simple method to identify the contribution of AC refrigerant to the SHED analyzer reading. R134A (CH2FCF3), the hydrofluorocarbon refrigerant used in all current automotive AC systems, as well as its predecessor, the chlorofluorocarbon R12, can be detected using the gas chromatography methods currently in place at many emissions labs for the speciation of exhaust and evaporative hydrocarbon emissions.

As vehicle tailpipe emission levels decrease with improvements in emission control technology and reformulation of gasolines, exhaust hydrocarbon levels begin to approach the levels in ambient air. Hydrocarbon speciation at these low levels requires high sensitivity capillary gas chromatography methods. In this study, a mixture of “synthetic” exhaust was prepared at two concentration levels (approximately 5 ppm C and 10 ppm C), and was analyzed by the widely-used Auto/Oil Air Quality Improvement Research Program (AQIRP) Phase II (gas chromatography) speciation method with a sensitivity of 0.005 ppm C for individual species. The mixture at each concentration level, along with a sample of ambient air, was analyzed a total of 20 times on 10 separate days over a 2½ week period. Concentrations of total hydrocarbons (HCs) and individual species (using the AQIRP library) were measured; averages and standard deviations were calculated.

A hydrocarbon trapping system for cold start emissions was constructed and tested using two types of carbonaceous adsorbents provided by Corning, Inc. One was made by combining activated carbon with an organic binder and extruding it into a honeycomb, and the other by depositing a carbon coating on a ceramic monolith. The tests were carried out on an engine in a dynamometer laboratory to characterize the performance of the carbon elements under transient cold start conditions. Performance was evaluated by continuously measuring exhaust gas hydrocarbon concentrations upstream and downstream of the trap, using conventional emissions consoles. Samples were also collected for off-line analysis of individual hydrocarbon species using gas chromatography to examine differences in adsorption of individual species. The speciated hydrocarbon data were used to distinguish between the mass trapping efficiency and a reactivity-based trapping efficiency of the adsorbant traps.

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.